Processes for preparing estolide base oils and oligomeric compounds that include cross metathesis

ABSTRACT

Provided herein are estolide base oils and oligomeric compounds prepared from processes that include cross metathesis. Exemplary processes include the preparation of terminally-unsaturated fatty acids by cross metathesis, and the subsequent oligomerization of terminally-unsaturated fatty acids to provide estolide compounds, such as the process set forth below:

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.13/707,480, filed Dec. 6, 2012, which claims the benefit under 35 U.S.C.§119(e) of U.S. Provisional Patent Application No. 61/577,598, filedDec. 19, 2011, and U.S. Provisional Patent Application No. 61/610,376,filed Mar. 13, 2012, both of which are incorporated herein by referencein their entireties for all purposes.

FIELD

The present disclosure relates to estolide base oils, oil stocks,lubricants, and oligomeric compounds, and methods of making the same.Exemplary processes include the use of cross metathesis.

BACKGROUND

Lubricant compositions typically comprise a base oil, such as ahydrocarbon base oil, and one or more additives. Estolides present apotential source of biobased, biodegradable oils that may be useful aslubricants and base stocks. In addition, certain oligomeric compounds,such as estolides prepared from fatty acids having terminal sites ofunsaturation, may provide biodegradable high-viscosity oils and otherpolymeric-type compounds.

SUMMARY

Described herein are estolide compounds and compositions, oligomericcompounds, and methods of making the same. In certain embodiments, suchcompounds and compositions may be useful as base oils and lubricants.Also described herein are oligomeric/polymeric compounds andcompositions that may be useful as high-viscosity oils or film-likematerials and coatings.

In certain embodiments are described at least one compound of Formula I:

wherein

x is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20;

y is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20;

n is an integer equal to or greater than 0;

R₁ is an optionally substituted alkyl that is saturated or unsaturated,and branched or unbranched; and

R₂ is selected from hydrogen and optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched;

wherein each fatty acid chain residue of said at least one compound isindependently optionally substituted, and wherein, for at least onefatty acid chain residue, x is an integer selected from 7 and 8 and y isan integer selected from 0, 1, 2, 3, 4, 5, and 6.

In certain embodiments are described at least one compound of FormulaII:

wherein

m is an integer equal to or greater than 1;

n is an integer equal to or greater than 0;

R₁ is an optionally substituted, branched or unbranched alkyl that issaturated or unsaturated;

R₂ is selected from hydrogen and optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched; and

R₃ and R₄, independently for each occurrence, are selected fromoptionally substituted alkyl that is saturated or unsaturated, andbranched or unbranched,

wherein at least one of R₁, R₃, and R₄ comprises an unbranched undecanylthat is saturated or unsaturated.

In certain embodiments are described a process of producing an estolidebase oil comprising:

providing at least one fatty acid substrate having at least one fattyacid residue with at least one internal site of unsaturation;

providing at least one alpha olefin;

contacting the at least one fatty acid substrate with the at least onealpha olefin in the presence of a metathesis catalyst to provide anolefin product and a metathesized fatty acid product;

optionally converting the metathesized fatty acid product into at leastone first fatty acid product;

optionally providing at least one second fatty acid reactant;

providing an oligomerization catalyst; and

oligomerizing the metathesized fatty acid product and/or first fattyacid product, optionally with the at least one second fatty acidreactant, in the presence of the oligomerization catalyst to produce anestolide base oil.

In certain embodiments the estolides comprise at least one compound ofFormula III:

wherein

n is an integer equal to or greater than 0;

R₁ is an optionally substituted, branched or unbranched alkyl that issaturated or unsaturated;

R₂ is selected from hydrogen and optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched; and

R₃ and R₄, independently for each occurrence, are selected from

-   -   wherein R₃ and R₄ are independently optionally substituted and z        is, independently for each occurrence, an integer selected from        0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,        18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33,        34, 35, 36, 37, 38, 39, and 40.

In certain embodiments are described a process of producing an estolidebase oil, comprising:

providing at least one estolide compound having at least one fatty acidchain residue with at least one internal site of unsaturation;

providing at least one olefin reactant; and

contacting the at least one estolide compound with the at least olefinreactant in the presence of a metathesis catalyst to provide an olefinproduct and an estolide base oil, wherein said estolide base oilcomprises at least one fatty acid chain residue with at least oneterminal site of unsaturation or at least one internal site ofunsaturation.

A process of producing an oligomeric compound is also described. Incertain embodiments, the process comprises:

providing at least one first fatty acid reactant and at least one secondfatty acid reactant, wherein the at least one second fatty acid reactanthas at least one terminal site of unsaturation; and

reacting the at least one first fatty acid reactant with the at leastone second fatty acid reactant to provide a compound, wherein a covalentbond is formed between an oxygen of a carboxylic group of the at leastone first fatty acid reactant and a carbon of the at least one terminalsite of unsaturation of the at least one second fatty acid reactant.

In certain embodiments, the estolides comprise at least one compound ofFormula V:

wherein

x is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20;

y is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20;

n is an integer equal to or greater than 0;

R₁ is an optionally substituted, branched or unbranched alkyl having atleast one terminal site of unsaturation; and

R₂ is selected from hydrogen and an optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched,

wherein each fatty acid chain residue of said at least one compound isindependently optionally substituted.

DETAILED DESCRIPTION

The use of lubricants and lubricant-containing compositions may resultin the dispersion of such fluids, compounds, and/or compositions in theenvironment. Petroleum base oils used in common lubricant compositions,as well as additives, are typically non-biodegradable and can be toxic.The present disclosure provides for the preparation and use ofcompositions comprising partially or fully biodegradable base oils,including base oils comprising one or more estolides.

In certain embodiments, the compositions comprising one or moreestolides are partially or fully biodegradable and thereby posediminished risk to the environment. In certain embodiments, thecompositions meet guidelines set for by the Organization for EconomicCooperation and Development (OECD) for degradation and accumulationtesting. The OECD has indicated that several tests may be used todetermine the “ready biodegradability” of organic chemicals. Aerobicready biodegradability by OECD 301D measures the mineralization of thetest sample to CO₂ in closed aerobic microcosms that simulate an aerobicaquatic environment, with microorganisms seeded from a waste-watertreatment plant. OECD 301D is considered representative of most aerobicenvironments that are likely to receive waste materials. Aerobic“ultimate biodegradability” can be determined by OECD 302D. Under OECD302D, microorganisms are pre-acclimated to biodegradation of the testmaterial during a pre-incubation period, then incubated in sealedvessels with relatively high concentrations of microorganisms andenriched mineral salts medium. OECD 302D ultimately determines whetherthe test materials are completely biodegradable, albeit under lessstringent conditions than “ready biodegradability” assays.

As used in the present specification, the following words, phrases andsymbols are generally intended to have the meanings as set forth below,except to the extent that the context in which they are used indicatesotherwise. The following abbreviations and terms have the indicatedmeanings throughout:

A dash (“-”) that is not between two letters or symbols is used toindicate a point of attachment for a substituent. For example, —C(O)NH₂is attached through the carbon atom.

“Alkoxy” by itself or as part of another substituent refers to a radical—OR³¹ where R³¹ is alkyl, cycloalkyl, cycloalkylalkyl, aryl, orarylalkyl, which can be substituted, as defined herein. In someembodiments, alkoxy groups have from 1 to 8 carbon atoms. In someembodiments, alkoxy groups have 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms.Examples of alkoxy groups include, but are not limited to, methoxy,ethoxy, propoxy, butoxy, cyclohexyloxy, and the like.

“Alkyl” by itself or as part of another substituent refers to asaturated or unsaturated, branched, or straight-chain monovalenthydrocarbon radical derived by the removal of one hydrogen atom from asingle carbon atom of a parent alkane, alkene, or alkyne. Examples ofalkyl groups include, but are not limited to, methyl; ethyls such asethanyl, ethenyl, and ethynyl; propyls such as propan-1-yl, propan-2-yl,prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl (allyl), prop-1-yn-1-yl,prop-2-yn-1-yl, etc.; butyls such as butan-1-yl, butan-2-yl,2-methyl-propan-1-yl, 2-methyl-propan-2-yl, but-1-en-1-yl,but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-1-yl, but-2-en-2-yl,buta-1,3-dien-1-yl, buta-1,3-dien-2-yl, but-1-yn-1-yl, but-1-yn-3-yl,but-3-yn-1-yl, etc.; and the like.

Unless otherwise indicated, the term “alkyl” is specifically intended toinclude groups having any degree or level of saturation, i.e., groupshaving exclusively single carbon-carbon bonds, groups having one or moredouble carbon-carbon bonds, groups having one or more triplecarbon-carbon bonds, and groups having mixtures of single, double, andtriple carbon-carbon bonds. Where a specific level of saturation isintended, the terms “alkanyl,” “alkenyl,” and “alkynyl” are used. Incertain embodiments, an alkyl group comprises from 1 to 40 carbon atoms,in certain embodiments, from 1 to 22 or 1 to 18 carbon atoms, in certainembodiments, from 1 to 16 or 1 to 8 carbon atoms, and in certainembodiments from 1 to 6 or 1 to 3 carbon atoms. In certain embodiments,an alkyl group comprises from 8 to 22 carbon atoms, in certainembodiments, from 8 to 18 or 8 to 16. In some embodiments, the alkylgroup comprises from 3 to 20 or 7 to 17 carbons. In some embodiments,the alkyl group comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 21, or 22 carbon atoms.

“Aryl” by itself or as part of another substituent refers to amonovalent aromatic hydrocarbon radical derived by the removal of onehydrogen atom from a single carbon atom of a parent aromatic ringsystem. Aryl encompasses 5- and 6-membered carbocyclic aromatic rings,for example, benzene; bicyclic ring systems wherein at least one ring iscarbocyclic and aromatic, for example, naphthalene, indane, andtetralin; and tricyclic ring systems wherein at least one ring iscarbocyclic and aromatic, for example, fluorene. Aryl encompassesmultiple ring systems having at least one carbocyclic aromatic ringfused to at least one carbocyclic aromatic ring, cycloalkyl ring, orheterocycloalkyl ring. For example, aryl includes 5- and 6-memberedcarbocyclic aromatic rings fused to a 5- to 7-membered non-aromaticheterocycloalkyl ring containing one or more heteroatoms chosen from N,O, and S. For such fused, bicyclic ring systems wherein only one of therings is a carbocyclic aromatic ring, the point of attachment may be atthe carbocyclic aromatic ring or the heterocycloalkyl ring. Examples ofaryl groups include, but are not limited to, groups derived fromaceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene,benzene, chrysene, coronene, fluoranthene, fluorene, hexacene,hexaphene, hexylene, as-indacene, s-indacene, indane, indene,naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene,pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene,picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene,trinaphthalene, and the like. In certain embodiments, an aryl group cancomprise from 5 to 20 carbon atoms, and in certain embodiments, from 5to 12 carbon atoms. In certain embodiments, an aryl group can comprise5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbonatoms. Aryl, however, does not encompass or overlap in any way withheteroaryl, separately defined herein. Hence, a multiple ring system inwhich one or more carbocyclic aromatic rings is fused to aheterocycloalkyl aromatic ring, is heteroaryl, not aryl, as definedherein.

“Arylalkyl” by itself or as part of another substituent refers to anacyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced withan aryl group. Examples of arylalkyl groups include, but are not limitedto, benzyl, 2-phenylethan-1-yl, 2-phenylethen-1-yl, naphthylmethyl,2-naphthylethan-1-yl, 2-naphthylethen-1-yl, naphthobenzyl,2-naphthophenylethan-1-yl, and the like. Where specific alkyl moietiesare intended, the nomenclature arylalkanyl, arylalkenyl, or arylalkynylis used. In certain embodiments, an arylalkyl group is C₇₋₃₀ arylalkyl,e.g., the alkanyl, alkenyl, or alkynyl moiety of the arylalkyl group isC₁₋₁₀ and the aryl moiety is C₆₋₂₀, and in certain embodiments, anarylalkyl group is C₇₋₂₀ arylalkyl, e.g., the alkanyl, alkenyl, oralkynyl moiety of the arylalkyl group is C₁₋₈ and the aryl moiety isC₆₋₁₂.

Estolide “base oil” and “base stock”, unless otherwise indicated, referto any composition comprising one or more estolide compounds. It shouldbe understood that an estolide “base oil” or “base stock” is not limitedto compositions for a particular use, and may generally refer tocompositions comprising one or more estolides, including mixtures ofestolides. Estolide base oils and base stocks can also include compoundsother than estolides.

The term “catalyst” refers to single chemical species; physicalcombinations of chemical species, such as mixtures, alloys, and thelike; and combinations of one or more catalyst within the same region orlocation of a reactor or reaction vessel. Examples of catalyst include,e.g., Lewis acids, Bronsted acids, and Bismuth catalysts, wherein Lewisacids, Bronsted acids, and Bismuth catalysts may be single chemicalspecies; physical combinations of chemical species, such as mixtures,alloys, and the like; and combinations of one or more catalyst withinthe same region or location of a reactor or reaction vessel.

“Compounds” refers to compounds encompassed by structural Formula I, II,III, IV, and V herein and includes any specific compounds within theformula whose structure is disclosed herein. Compounds may be identifiedeither by their chemical structure and/or chemical name. When thechemical structure and chemical name conflict, the chemical structure isdeterminative of the identity of the compound. The compounds describedherein may contain one or more chiral centers and/or double bonds andtherefore may exist as stereoisomers such as double-bond isomers (i.e.,geometric isomers), enantiomers, or diastereomers. Accordingly, anychemical structures within the scope of the specification depicted, inwhole or in part, with a relative configuration encompass all possibleenantiomers and stereoisomers of the illustrated compounds including thestereoisomerically pure form (e.g., geometrically pure, enantiomericallypure, or diastereomerically pure) and enantiomeric and stereoisomericmixtures. Enantiomeric and stereoisomeric mixtures may be resolved intotheir component enantiomers or stereoisomers using separation techniquesor chiral synthesis techniques well known to the skilled artisan.

For the purposes of the present disclosure, “chiral compounds” arecompounds having at least one center of chirality (i.e. at least oneasymmetric atom, in particular at least one asymmetric C atom), havingan axis of chirality, a plane of chirality or a screw structure.“Achiral compounds” are compounds which are not chiral.

Compounds of Formula I, II, III, IV, and V include, but are not limitedto, optical isomers of compounds of Formula I, II, III, IV, and V,racemates thereof, and other mixtures thereof. In such embodiments, thesingle enantiomers or diastereomers, i.e., optically active forms, canbe obtained by asymmetric synthesis or by resolution of the racemates.Resolution of the racemates may be accomplished by, for example,chromatography, using, for example a chiral high-pressure liquidchromatography (HPLC) column. However, unless otherwise stated, itshould be assumed that Formula I, II, III, IV, and V cover allasymmetric variants of the compounds described herein, includingisomers, racemates, enantiomers, diastereomers, and other mixturesthereof. In addition, compounds of Formula I, II, III, IV, and V includeZ- and E-forms (e.g., cis- and trans-forms) of compounds with doublebonds. The compounds of Formula I, II, III, IV, and V may also exist inseveral tautomeric forms including the enol form, the keto form, andmixtures thereof. Accordingly, the chemical structures depicted hereinencompass all possible tautomeric forms of the illustrated compounds.

“Cycloalkyl” by itself or as part of another substituent refers to asaturated or unsaturated cyclic alkyl radical. Where a specific level ofsaturation is intended, the nomenclature “cycloalkanyl” or“cycloalkenyl” is used. Examples of cycloalkyl groups include, but arenot limited to, groups derived from cyclopropane, cyclobutane,cyclopentane, cyclohexane, and the like. In certain embodiments, acycloalkyl group is C₃₋₁₅ cycloalkyl, and in certain embodiments, C₃₋₁₂cycloalkyl or C₅₋₁₂ cycloalkyl. In certain embodiments, a cycloalkylgroup is a C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, or C₁₅cycloalkyl.

“Cycloalkylalkyl” by itself or as part of another substituent refers toan acyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced with acycloalkyl group. Where specific alkyl moieties are intended, thenomenclature cycloalkylalkanyl, cycloalkylalkenyl, or cycloalkylalkynylis used. In certain embodiments, a cycloalkylalkyl group is C₇₋₃₀cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of thecycloalkylalkyl group is C₁₋₁₀ and the cycloalkyl moiety is C₆₋₂₀, andin certain embodiments, a cycloalkylalkyl group is C₇₋₂₀cycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety of thecycloalkylalkyl group is C₁₋₈ and the cycloalkyl moiety is C₄₋₂₀ orC₆₋₁₂.

“Halogen” refers to a fluoro, chloro, bromo, or iodo group.

“Heteroaryl” by itself or as part of another substituent refers to amonovalent heteroaromatic radical derived by the removal of one hydrogenatom from a single atom of a parent heteroaromatic ring system.Heteroaryl encompasses multiple ring systems having at least onearomatic ring fused to at least one other ring, which can be aromatic ornon-aromatic in which at least one ring atom is a heteroatom. Heteroarylencompasses 5- to 12-membered aromatic, such as 5- to 7-membered,monocyclic rings containing one or more, for example, from 1 to 4, or incertain embodiments, from 1 to 3, heteroatoms chosen from N, O, and S,with the remaining ring atoms being carbon; and bicyclicheterocycloalkyl rings containing one or more, for example, from 1 to 4,or in certain embodiments, from 1 to 3, heteroatoms chosen from N, O,and S, with the remaining ring atoms being carbon and wherein at leastone heteroatom is present in an aromatic ring. For example, heteroarylincludes a 5- to 7-membered heterocycloalkyl, aromatic ring fused to a5- to 7-membered cycloalkyl ring. For such fused, bicyclic heteroarylring systems wherein only one of the rings contains one or moreheteroatoms, the point of attachment may be at the heteroaromatic ringor the cycloalkyl ring. In certain embodiments, when the total number ofN, S, and O atoms in the heteroaryl group exceeds one, the heteroatomsare not adjacent to one another. In certain embodiments, the totalnumber of N, S, and O atoms in the heteroaryl group is not more thantwo. In certain embodiments, the total number of N, S, and O atoms inthe aromatic heterocycle is not more than one. Heteroaryl does notencompass or overlap with aryl as defined herein.

Examples of heteroaryl groups include, but are not limited to, groupsderived from acridine, arsindole, carbazole, β-carboline, chromane,chromene, cinnoline, furan, imidazole, indazole, indole, indoline,indolizine, isobenzofuran, isochromene, isoindole, isoindoline,isoquinoline, isothiazole, isoxazole, naphthyridine, oxadiazole,oxazole, perimidine, phenanthridine, phenanthroline, phenazine,phthalazine, pteridine, purine, pyran, pyrazine, pyrazole, pyridazine,pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline,quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole, thiophene,triazole, xanthene, and the like. In certain embodiments, a heteroarylgroup is from 5- to 20-membered heteroaryl, and in certain embodimentsfrom 5- to 12-membered heteroaryl or from 5- to 10-membered heteroaryl.In certain embodiments, a heteroaryl group is a 5-, 6-, 7-, 8-, 9-, 10-,11-, 12-, 13-, 14-, 15-, 16-, 17-, 18-, 19-, or 20-membered heteroaryl.In certain embodiments heteroaryl groups are those derived fromthiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine,quinoline, imidazole, oxazole, and pyrazine.

“Heteroarylalkyl” by itself or as part of another substituent refers toan acyclic alkyl radical in which one of the hydrogen atoms bonded to acarbon atom, typically a terminal or sp³ carbon atom, is replaced with aheteroaryl group. Where specific alkyl moieties are intended, thenomenclature heteroarylalkanyl, heteroarylalkenyl, or heteroarylalkynylis used. In certain embodiments, a heteroarylalkyl group is a 6- to30-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynylmoiety of the heteroarylalkyl is 1- to 10-membered and the heteroarylmoiety is a 5- to 20-membered heteroaryl, and in certain embodiments, 6-to 20-membered heteroarylalkyl, e.g., the alkanyl, alkenyl, or alkynylmoiety of the heteroarylalkyl is 1- to 8-membered and the heteroarylmoiety is a 5- to 12-membered heteroaryl.

“Heterocycloalkyl” by itself or as part of another substituent refers toa partially saturated or unsaturated cyclic alkyl radical in which oneor more carbon atoms (and any associated hydrogen atoms) areindependently replaced with the same or different heteroatom. Examplesof heteroatoms to replace the carbon atom(s) include, but are notlimited to, N, P, O, S, Si, etc. Where a specific level of saturation isintended, the nomenclature “heterocycloalkanyl” or “heterocycloalkenyl”is used. Examples of heterocycloalkyl groups include, but are notlimited to, groups derived from epoxides, azirines, thiiranes,imidazolidine, morpholine, piperazine, piperidine, pyrazolidine,pyrrolidine, quinuclidine, and the like.

“Heterocycloalkylalkyl” by itself or as part of another substituentrefers to an acyclic alkyl radical in which one of the hydrogen atomsbonded to a carbon atom, typically a terminal or sp³ carbon atom, isreplaced with a heterocycloalkyl group. Where specific alkyl moietiesare intended, the nomenclature heterocycloalkylalkanyl,heterocycloalkylalkenyl, or heterocycloalkylalkynyl is used. In certainembodiments, a heterocycloalkylalkyl group is a 6- to 30-memberedheterocycloalkylalkyl, e.g., the alkanyl, alkenyl, or alkynyl moiety ofthe heterocycloalkylalkyl is 1- to 10-membered and the heterocycloalkylmoiety is a 5- to 20-membered heterocycloalkyl, and in certainembodiments, 6- to 20-membered heterocycloalkylalkyl, e.g., the alkanyl,alkenyl, or alkynyl moiety of the heterocycloalkylalkyl is 1- to8-membered and the heterocycloalkyl moiety is a 5- to 12-memberedheterocycloalkyl.

“Mixture” refers to a collection of molecules or chemical substances.Each component in a mixture can be independently varied. A mixture maycontain, or consist essentially of, two or more substances intermingledwith or without a constant percentage composition, wherein eachcomponent may or may not retain its essential original properties, andwhere molecular phase mixing may or may not occur. In mixtures, thecomponents making up the mixture may or may not remain distinguishablefrom each other by virtue of their chemical structure.

“Parent aromatic ring system” refers to an unsaturated cyclic orpolycyclic ring system having a conjugated π (pi) electron system.Included within the definition of “parent aromatic ring system” arefused ring systems in which one or more of the rings are aromatic andone or more of the rings are saturated or unsaturated, such as, forexample, fluorene, indane, indene, phenalene, etc. Examples of parentaromatic ring systems include, but are not limited to, aceanthrylene,acenaphthylene, acephenanthrylene, anthracene, azulene, benzene,chrysene, coronene, fluoranthene, fluorene, hexacene, hexaphene,hexylene, as-indacene, s-indacene, indane, indene, naphthalene,octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene,pentalene, pentaphene, perylene, phenalene, phenanthrene, picene,pleiadene, pyrene, pyranthrene, rubicene, triphenylene, trinaphthalene,and the like.

“Parent heteroaromatic ring system” refers to a parent aromatic ringsystem in which one or more carbon atoms (and any associated hydrogenatoms) are independently replaced with the same or different heteroatom.Examples of heteroatoms to replace the carbon atoms include, but are notlimited to, N, P, O, S, Si, etc. Specifically included within thedefinition of “parent heteroaromatic ring systems” are fused ringsystems in which one or more of the rings are aromatic and one or moreof the rings are saturated or unsaturated, such as, for example,arsindole, benzodioxan, benzofuran, chromane, chromene, indole,indoline, xanthene, etc. Examples of parent heteroaromatic ring systemsinclude, but are not limited to, arsindole, carbazole, β-carboline,chromane, chromene, cinnoline, furan, imidazole, indazole, indole,indoline, indolizine, isobenzofuran, isochromene, isoindole,isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine,oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline,phenazine, phthalazine, pteridine, purine, pyran, pyrazine, pyrazole,pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine, quinazoline,quinoline, quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole,thiophene, triazole, xanthene, and the like.

“Solid-supported acid” refers to an acidic compound or material that issupported by or attached to another compound or material comprising asolid or semi-solid structure. Such materials include smooth supports(e.g., metal, glass, plastic, silicon, carbon (e.g., diamond, graphite,nanotubes, fullerenes (e.g., C-60)) and ceramic surfaces) as well astextured and porous materials such as clays and clay-like materials.Such materials also include, but are not limited to, gels, rubbers,polymers, and other non-rigid materials. Solid supports need not becomposed of a single material. By way of example but not by way oflimitation, a solid support may comprise a surface material (e.g. alayer or coating) and a different supporting material (e.g., coatedglass, coated metals and plastics, etc.) In some embodiments,solid-supported acids comprise two or more different materials, e.g., inlayers. Surface layers and coatings may be of any configuration and maypartially or completely cover a supporting material. It is contemplatedthat solid supports may comprise any combination of layers, coatings, orother configurations of multiple materials. In some embodiments, asingle material provides essentially all of the surface to which othermaterial can be attached, while in other embodiments, multiple materialsof the solid support are exposed for attachment of another material.Solid supports need not be flat. Supports include any type of shapeincluding spherical shapes (e.g., beads). Acidic moieties attached tosolid support may be attached to any portion of the solid support (e.g.,may be attached to an interior portion of a porous solid supportmaterial). Exemplary solid-supported acids include, but are not limitedto, cation exchange resins (e.g., Amberlyst®, Dowex®); acid-activatedclays (e.g., montmorillonites); polymer-supported sulfonic acids (e.g.,Nafion®); and silica-support catalysts (e.g., SPA-2).

“Substituted” refers to a group in which one or more hydrogen atoms areindependently replaced with the same or different substituent(s).Examples of substituents include, but are not limited to, —R″, —R⁶⁰,—O⁻, —OH, ═O, —OR⁶⁰, —SR⁶⁰, —S⁻, ═S, —NR⁶⁰R⁶¹, ═NR⁶⁰, —CN, —CF₃, —OCN,—SCN, —NO, —NO₂, ═N₂, —N₃, —S(O)₂O⁻, —S(O)₂OH, —S(O)₂R⁶⁰, —OS(O₂)O⁻,—OS(O)₂R⁶⁰—P(O)(OR⁶⁰)(O⁻), —OP(O)(OR⁶⁰)(OR⁶¹), —C(O)R⁶⁰, —C(S)R⁶⁰,—C(O)OR⁶⁰, —C(O)NR⁶⁰R⁶¹, —C(O)O⁻, —C(S)OR⁶⁰, —NR⁶²C(O)NR⁶⁰R⁶¹,—NR⁶²C(S)NR⁶⁰R⁶¹, —NR⁶²C(NR⁶³)NR⁶⁰R⁶¹, —C(NR⁶²)NR⁶⁰R⁶¹, —S(O)₂, NR⁶⁰R⁶¹,—NR⁶³S(O)₂R⁶⁰, —NR⁶³C(O)R⁶⁰, and —S(O)R⁶⁰;

wherein each —R⁶⁴ is independently a halogen; each R⁶⁰ and R⁶¹ areindependently alkyl, substituted alkyl, alkoxy, substituted alkoxy,cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, aryl, substituted aryl, heteroaryl, substitutedheteroaryl, arylalkyl, substituted arylalkyl, heteroarylalkyl, orsubstituted heteroarylalkyl, or R⁶⁰ and R⁶¹ together with the nitrogenatom to which they are bonded form a heterocycloalkyl, substitutedheterocycloalkyl, heteroaryl, or substituted heteroaryl ring, and R⁶²and R⁶³ are independently alkyl, substituted alkyl, aryl, substitutedaryl, arylalkyl, substituted arylalkyl, cycloalkyl, substitutedcycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, heteroaryl,substituted heteroaryl, heteroarylalkyl, or substituted heteroarylalkyl,or R⁶² and R⁶³ together with the atom to which they are bonded form oneor more heterocycloalkyl, substituted heterocycloalkyl, heteroaryl, orsubstituted heteroaryl rings;

wherein the “substituted” substituents, as defined above for R⁶⁰, R⁶¹,R⁶², and R⁶³, are substituted with one or more, such as one, two, orthree, groups independently selected from alkyl, -alkyl-OH,—O-haloalkyl, -alkyl-NH₂, alkoxy, cycloalkyl, cycloalkylalkyl,heterocycloalkyl, heterocycloalkylalkyl, aryl, heteroaryl, arylalkyl,heteroarylalkyl, —O⁻, —OH, ═O, —O-alkyl, —O-aryl, —O-heteroarylalkyl,—O-cycloalkyl, —O-heterocycloalkyl, —SH, —S⁻, ═S, —S-alkyl, —S-aryl,—S-heteroarylalkyl, —S-cycloalkyl, —S-heterocycloalkyl, —NH₂, ═NH, —CN,—CF₃, —OCN, —SCN, —NO, —NO₂, ═N₂, —N₃, —S(O)₂O, —S(O)₂, —S(O)₂OH,—OS(O₂)O, —SO₂(alkyl), —SO₂(phenyl), —SO₂(haloalkyl), —SO₂NH₂,—SO₂NH(alkyl), —SO₂NH(phenyl), —P(O)(O⁻)₂, —P(O)(O-alkyl)(O⁻),—OP(O)(O-alkyl)(O-alkyl), —CO₂H, —C(O)O(alkyl), —CON(alkyl)(alkyl),—CONH(alkyl), —CONH₂, —C(O)(alkyl), —C(O)(phenyl), —C(O)(haloalkyl),—OC(O)(alkyl), —N(alkyl)(alkyl), —NH(alkyl), —N(alkyl)(alkylphenyl),—NH(alkylphenyl), —NHC(O)(alkyl), —NHC(O)(phenyl), —N(alkyl)C(O)(alkyl),and —N(alkyl)C(O)(phenyl).

As used in this specification and the appended claims, the articles “a,”“an,” and “the” include plural referents unless expressly andunequivocally limited to one referent.

The term “fatty acid” refers to any natural or synthetic carboxylic acidcomprising an alkyl chain that may be saturated, monounsaturated, orpolyunsaturated, and may have straight or branched chains. The fattyacid may also be substituted. “Fatty acid,” as used herein, includesshort chain alkyl carboxylic acids including, for example, acetic acid,propionic acid, etc.

The terms “fatty acid reactant”, “fatty acid product” and “fatty acidsubstrate” refer to any compound or composition comprising at least onefatty acid residue. For example, in certain embodiments, the fatty acidreactant or product may comprise a saturated or unsaturated fatty acid,fatty acid alkyl ester (e.g., methyl stearate, 9-dodecenoic acid methylester), fatty acid glyceride (e.g., triglyceride, monoglyceride), orfatty acid oligomer. In certain embodiments, a fatty acid oligomer maycomprise a first fatty acid that has previously undergoneoligomerization with one or more second fatty acids to form an estolide,such as an estolide having a low EN (e.g., dimer). In certainembodiments, that fatty acid reactant or product is capable ofundergoing oligomerization with another fatty acid or fatty acidreactant. For example, the fatty acid reactant or product may comprise afatty acid residue having at least one site of unsaturation and, thus,may be capable of undergoing oligomerization with another fatty acidreactant or product (e.g., saturated or unsaturated fatty acid). It isunderstood that a “first” fatty acid reactant can comprise the samestructure as a first fatty acid “product” or a “second” fatty acidreactant. For example, in certain embodiments, a reaction mixture mayonly comprise oleic acid, wherein the first fatty acid reactant andsecond fatty acid reactant are both oleic acid.

The term “acid-activated clay” refers to clays that are derived from thenaturally occurring ore bentonite or the mineral montmorillonite andincludes materials prepared by calcination, washing or leaching withmineral acid, ion exchange or any combination thereof, includingmaterials which are often called montmorillonites, acid-activatedmontmorillonites and activated montmorillonites. In certain embodiments,these clays may contain Bronsted as well as Lewis acid active sites withmany of the acidic sites located within the clay lattice. Such claysinclude, but are not limited to the materials denoted as montmorilloniteK10, montmorillonite clay, clayzic, clayfen, the Engelhardt series ofcatalysts related to and including X-9107, X9105, Girdler KSF, Tonsiland K-catalysts derived from montmorillonite, including but not limitedto K5, K10, K20 and K30, KSF, KSF/O, and KP10. Other acid-activatedclays may include X-9105 and X-9107 acid washed clay catalysts marketedby Engelhard.

The term “zeolite” refers to mesoporous aluminosilicates of the group IAor group IIA elements and are related to montmorillonite clays that areor have been acid activated. Zeolites may comprise what is considered an“infinitely” extending framework of AlO₄ and SiO₄ tetrahedra linked toeach other by the sharing of oxygens. The framework structure maycontain channels or interconnecting voids that are occupied by cationsand water molecules. Acidic character may be imparted or enhanced by ionexchange of the cations, such as with ammonium ions and subsequentthermal deamination or calcination. The acidic sites may primarily belocated within the lattice pores and channels. In certain instances,zeolites include, but are not limited to, the beta-type zeolites astypified by CP814E manufactured by Zeolyst International, the mordeniteform of zeolites as typified by CBV21A manufactured by ZeolystInternational, the Y-type zeolites as typified by CBV-720 manufacturedby Zeolyst International, and the ZSM family of zeolites as typified byZSM-5, and ZSM-11.

All numerical ranges herein include all numerical values and ranges ofall numerical values within the recited range of numerical values.

The present disclosure relates to estolide compounds,oligomeric/polymeric compounds and high-viscosity compositions thereof,and methods of making the same. In certain embodiments, the presentdisclosure also relates to polymeric compounds, such as estolidesprepared from fatty acids having terminal sites of unsaturation, thatare useful as high-viscosity oils or exhibit other unique properties(e.g., film-forming; lacquers; hardened coatings). In certainembodiments, the present disclosure relates to biosynthetic estolideshaving desired viscometric properties, while retaining or even improvingother properties such as oxidative stability and pour point. In certainembodiments, new methods of preparing estolide compounds exhibiting suchproperties are provided. The present disclosure also relates tocompositions comprising certain estolide compounds exhibiting suchproperties.

In certain embodiments are described at least one compound of Formula I:

wherein

x is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20;

y is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20;

n is an integer equal to or greater than 0;

R₁ is an optionally substituted alkyl that is saturated or unsaturated,and branched or unbranched; and

R₂ is selected from hydrogen and an optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched;

wherein each fatty acid chain residue of said at least one compound isindependently optionally substituted, and wherein, for at least onefatty acid chain residue, x is an integer selected from 7 and 8 and y isan integer selected from 0, 1, 2, 3, 4, 5, and 6.

In certain embodiments are described at least one compound of FormulaII:

wherein

m is an integer equal to or greater than 1;

n is an integer equal to or greater than 0;

R₁ is an optionally substituted, branched or unbranched alkyl that issaturated or unsaturated;

R₂ is selected from hydrogen and optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched; and

R₃ and R₄, independently for each occurrence, are selected fromoptionally substituted alkyl that is saturated or unsaturated, andbranched or unbranched, wherein at least one of R₁, R₃, and R₄ comprisesan unbranched undecanyl that is saturated or unsaturated.

In certain embodiments, the process of producing an estolide base oilcomprises:

providing at least one fatty acid substrate having at least one fattyacid residue with at least one internal site of unsaturation;

providing at least one alpha olefin;

contacting the at least one fatty acid substrate with the at least onealpha olefin in the presence of a metathesis catalyst to provide anolefin product and a metathesized fatty acid product;

optionally converting the metathesized fatty acid product into at leastone first fatty acid product;

optionally providing at least one second fatty acid reactant;

providing an oligomerization catalyst; and

oligomerizing the metathesized fatty acid product and/or first fattyacid product, optionally with the at least one second fatty acidreactant, in the presence of the oligomerization catalyst to produce anestolide base oil.

In certain embodiments are described compounds of Formula III:

wherein

n is an integer equal to or greater than 0;

R₁ is an optionally substituted, branched or unbranched alkyl that issaturated or unsaturated;

R₂ is selected from hydrogen and optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched; and

R₃ and R₄, independently for each occurrence, are selected from

-   -   wherein R₃ and R₄ are independently optionally substituted and z        is, independently for each occurrence, an integer selected from        0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,        18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33,        34, 35, 36, 37, 38, 39, and 40.

In certain embodiments are described a process of producing an estolidebase oil, comprising:

providing at least one estolide compound having at least one fatty acidchain residue with at least one internal site of unsaturation;

providing at least one olefin reactant; and

contacting the at least one estolide compound with the at least olefinreactant in the presence of a metathesis catalyst to provide an olefinproduct and an estolide base oil, wherein said estolide base oilcomprises at least one fatty acid chain residue with at least oneterminal site of unsaturation or at least one internal site ofunsaturation.

A process of producing an oligomeric compound is also described. Incertain embodiments, the process comprises:

providing at least one first fatty acid reactant and at least one secondfatty acid reactant, wherein the at least one second fatty acid reactanthas at least one terminal site of unsaturation; and

reacting the at least one first fatty acid reactant with the at leastone second fatty acid reactant to provide a compound, wherein a covalentbond is formed between an oxygen of a carboxylic group of the at leastone first fatty acid reactant and a carbon of the at least one terminalsite of unsaturation of the at least one second fatty acid reactant.

In certain embodiments, the estolides comprise at least one compound ofFormula V:

wherein

x is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20;

y is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20;

n is an integer equal to or greater than 0;

R₁ is an optionally substituted, branched or unbranched alkyl having atleast one terminal site of unsaturation; and

R₂ is selected from hydrogen and an optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched,

wherein each fatty acid chain residue of said at least one compound isindependently optionally substituted.

In certain embodiments, the composition comprises at least one estolideof Formula I, II, or III where R₁ is hydrogen.

The terms “chain” or “fatty acid chain” or “fatty acid chain residue,”as used with respect to the compounds of Formula I, II, III, and V,refer to one or more of the fatty acid residues incorporated incompounds, e.g., R₃ or R₄ of Formula II and III, or the structuresrepresented by CH₃(CH₂)_(y)CH(CH₂)_(x)C(O)O— in Formula I and V.

The R₁ in Formula I, II, III, and V at the top of each Formula shown isan example of what may be referred to as a “cap” or “capping material,”as it “caps” the top of the compound. Similarly, the capping group maybe an organic acid residue of general formula —OC(O)-alkyl, i.e., acarboxylic acid with a substituted or unsubstituted, saturated orunsaturated, and/or branched or unbranched alkyl as defined herein, or aformic acid residue. In certain embodiments, the “cap” or “cappinggroup” is a fatty acid. In certain embodiments, the capping group,regardless of size, is substituted or unsubstituted, saturated orunsaturated, and/or branched or unbranched. In certain embodiments, thecapping group comprises an alkyl group with at least one terminal siteof unsaturation. As described in further detail below, in certainembodiments, an alkyl capping group with at least one terminal site ofunsaturation may be prepared by subjecting an estolide initially havingan alkyl capping group with at least one internal site of unsaturationto cross metathesis conditions. Alternatively, in certain embodiments, acompound with an alkyl capping group having at least one terminal siteof unsaturation may be prepared by oligomerizing/polymerizing two ormore fatty acid reactants having terminal sites of unsaturation. The capor capping material may also be referred to as the primary or alpha (α)chain.

Depending on the manner in which the compound is synthesized, the cap orcapping group alkyl may be the only alkyl from an organic acid residuein the resulting estolide that is unsaturated. In certain embodiments,it may be desirable to use a saturated organic or fatty-acid cap toincrease the overall saturation of the estolide and/or to increase theresulting estolide's stability. For example, in certain embodiments, itmay be desirable to provide a method of providing a saturated cappedestolide by hydrogenating an unsaturated cap using any suitable methodsavailable to those of ordinary skill in the art. Hydrogenation may beused with various sources of the fatty-acid feedstock, which may includemono- and/or polyunsaturated fatty acids. Without being bound to anyparticular theory, in certain embodiments, hydrogenating the estolidemay help to improve the overall stability of the molecule. However, afully-hydrogenated estolide, such as an estolide with a larger fattyacid cap, may exhibit increased pour point temperatures. In certainembodiments, it may be desirable to offset any loss in desirablepour-point characteristics by using shorter, saturated cappingmaterials. In certain embodiments, this may be accomplished by cleavingan estolide at its internal site of unsaturation (e.g., oleic cap) witha metathesis catalyst to provide a shorter cap (C₁₀) having a terminalsite of unsaturation. In addition, or in the alternative, as describedfurther below, it may be desirable to add further functionalization tothe compound by altering the structure of the compound at a site ofunsaturation, such as altering the structure of the compound at aterminal site of unsaturation in an alkyl capping group.

The R₄C(O)O— of Formula II and III, or structureCH₃(CH₂)_(y)CH(CH₂)_(x)C(O)O— of Formula I and V, serve as the “base” or“base chain residue” of the estolide. Depending on the manner in whichthe compound is synthesized, the base organic acid or fatty acid residuemay be the only residue that remains in its free-acid form after theinitial synthesis of the compound. However, in certain embodiments, inan effort to alter or improve the properties of the compound, the freeacid may be reacted with any number of substituents. For example, it maybe desirable to react the free acid compound with alcohols, glycols,amines, or other suitable reactants to provide the corresponding ester,amide, or other reaction products. The base or base chain residue mayalso be referred to as tertiary or gamma (γ) chains.

The R₃C(O)O— of Formula II and III, or structureCH₃(CH₂)_(y)CH(CH₂)_(x)C(O)O— of Formula I and V, are linking residuesthat link the capping material and the base fatty-acid residue together.There may be any number of linking residues in the estolide, includingwhen n=0 and the estolide is in its dimer form. Depending on the mannerin which the compound is prepared, a linking residue may be a fatty acidand may initially be in an unsaturated form during synthesis. In someembodiments, the compound will be formed when a catalyst is used toproduce a carbocation at the fatty acid's site of unsaturation, which isfollowed by nucleophilic attack on the carbocation by the carboxylicgroup of another fatty acid. In some embodiments, it may be desirable tohave a linking fatty acid that is monounsaturated so that when the fattyacids link together, all of the sites of unsaturation are eliminated.The linking residue(s) may also be referred to as secondary or beta (β)chains.

In certain embodiments, the cap is an acetyl group, the linkingresidue(s) is one or more fatty acid residues, and the base chainresidue is a fatty acid residue. In certain embodiments, the linkingresidues present in a compound differ from one another. In certainembodiments, one or more of the linking residues differs from the basechain residue.

As noted above, in certain embodiments, suitable unsaturated fatty acidsfor preparing the compounds may include any mono- or polyunsaturatedfatty acid. For example, monounsaturated fatty acids, along with asuitable catalyst, will form a single carbocation that allows for theaddition of a second fatty acid, whereby a single link between two fattyacids is formed. Suitable monounsaturated fatty acids may include, butare not limited to, palmitoleic acid (16:1), vaccenic acid (18:1), oleicacid (18:1), eicosenoic acid (20:1), erucic acid (22:1), and nervonicacid (24:1). In addition, in certain embodiments, polyunsaturated fattyacids may be used to create estolides. Suitable polyunsaturated fattyacids may include, but are not limited to, hexadecatrienoic acid (16:3),alpha-linolenic acid (18:3), stearidonic acid (18:4), eicosatrienoicacid (20:3), eicosatetraenoic acid (20:4), eicosapentaenoic acid (20:5),heneicosapentaenoic acid (21:5), docosapentaenoic acid (22:5),docosahexaenoic acid (22:6), tetracosapentaenoic acid (24:5),tetracosahexaenoic acid (24:6), linoleic acid (18:2), gamma-linoleicacid (18:3), eicosadienoic acid (20:2), dihomo-gamma-linolenic acid(20:3), arachidonic acid (20:4), docosadienoic acid (20:2), adrenic acid(22:4), docosapentaenoic acid (22:5), tetracosatetraenoic acid (22:4),tetracosapentaenoic acid (24:5), pinolenic acid (18:3), podocarpic acid(20:3), rumenic acid (18:2), alpha-calendic acid (18:3), beta-calendicacid (18:3), jacaric acid (18:3), alpha-eleostearic acid (18:3),beta-eleostearic (18:3), catalpic acid (18:3), punicic acid (18:3),rumelenic acid (18:3), alpha-parinaric acid (18:4), beta-parinaric acid(18:4), and bosseopentaenoic acid (20:5). In certain embodiments,hydroxy fatty acids may be polymerized or homopolymerized by reactingthe carboxylic acid functionality of one fatty acid with the hydroxyfunctionality of a second fatty acid. Exemplary hydroxyl fatty acidsinclude, but are not limited to, ricinoleic acid, 6-hydroxystearic acid,9,10-dihydroxystearic acid, 12-hydroxystearic acid, and14-hydroxystearic acid.

The process for preparing the compounds described herein may include theuse of any natural or synthetic fatty acid source. However, it may bedesirable to source the fatty acids from a renewable biologicalfeedstock. Suitable starting materials of biological origin may includeplant fats, plant oils, plant waxes, animal fats, animal oils, animalwaxes, fish fats, fish oils, fish waxes, algal oils and mixturesthereof. Other potential fatty acid sources may include waste andrecycled food-grade fats and oils, fats, oils, and waxes obtained bygenetic engineering, fossil fuel-based materials and other sources ofthe materials desired.

In certain embodiments, the compounds described herein may be preparedfrom non-naturally occurring fatty acids derived from naturallyoccurring feedstocks. In certain embodiments, the compounds are preparedfrom synthetic fatty acid products derived from naturally occurringfeedstocks such as vegetable oils. For example, the synthetic fatty acidproduct may be prepared by cleaving fragments from larger fatty acidresidues occurring in natural oils, such as triglycerides, using any ofthe suitable metathesis processes described further below. In certainembodiments, the resulting truncated fatty acid residue(s) may then beliberated from the glycerine backbone using any suitable hydrolyticand/or transesterification processes known to those of skill in the art.An exemplary fatty acid product includes 9-dodecenoic acid, which may beprepared via the cross metathesis of an oleic acid residue with1-butene. In certain embodiments, the naturally-occurring fatty acid maybe liberated from the glycerine backbone prior to being exposed tometathesis. Such metathesis reactions may be non-specific and producemixtures of products, wherein reactions producing, for example,internally-unsaturated fatty acids such as 9-dodecenoic acid alsoproduce varying amounts of the terminally-unsaturated fatty acid,9-decenoic acid. In certain embodiments, it may be desirable to optimizethe production of fatty acids having at least one terminal site ofunsaturation by reacting an unsaturated fatty acid reactant (e.g., oleicacid) with ethylene under metathesis conditions, whereby theterminally-unsaturated fatty acid product (e.g., 9-decenoic acid) isproduced exclusively.

In some embodiments, the compound comprises fatty-acid chains of varyinglengths. In some embodiments, x is, independently for each occurrence,an integer selected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 1 to 12, 1to 10, 2 to 8, 6 to 8, or 4 to 6. In some embodiments, x is,independently for each occurrence, an integer selected from 7 and 8. Insome embodiments, x is, independently for each occurrence, an integerselected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, and 20. In certain embodiments, for at least one fatty acidchain residue, x is an integer selected from 7 and 8.

In some embodiments, y is, independently for each occurrence, an integerselected from 0 to 20, 0 to 18, 0 to 16, 0 to 14, 1 to 12, 1 to 10, 2 to8, 6 to 8, or 4 to 6. In some embodiments, y is, independently for eachoccurrence, an integer selected from 7 and 8. In some embodiments, y is,independently for each occurrence, an integer selected from 0, 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. Incertain embodiments, for at least one fatty acid chain residue, y is aninteger selected from 7 and 8. In some embodiments, for at least onefatty acid chain residue, y is an integer selected from 0 to 6, or 1 and2. In certain embodiments, y is, independently for each occurrence, aninteger selected from 1 to 6, or 1 and 2.

In some embodiments, x+y is, independently for each chain, an integerselected from 0 to 40, 0 to 20, 10 to 20, or 12 to 18. In someembodiments, x+y is, independently for each chain, an integer selectedfrom 13 to 15. In some embodiments, x+y is 15. In some embodiments, x+yis, independently for each chain, an integer selected from 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and 24. Incertain embodiments, x+y, independently for each chain, is an integerselected from 5 to 15. In certain embodiments, for at least one fattyacid chain residue, x+y is 7. In certain embodiments, x+y is 7 for eachfatty acid chain residue. In certain embodiments, for at least one fattyacid chain residue, x+y is an integer selected from 9 to 13. In certainembodiments, for at least one fatty acid chain residue, x+y is 9. Incertain embodiments, x+y is, independently for each chain, an integerselected from 9 to 13. In certain embodiments, x+y is 9 for each fattyacid chain residue.

In some embodiments, the estolide compound of Formula I, II, III, and Vmay comprise any number of fatty acid residues to form an “n-mer”estolide. For example, the compound may be in its dimer (n=0), trimer(n=1), tetramer (n=2), pentamer (n=3), hexamer (n=4), heptamer (n=5),octamer (n=6), nonamer (n=7), or decamer (n=8) form. In someembodiments, n is an integer selected from 0 to 20, 0 to 18, 0 to 16, 0to 14, 0 to 12, 0 to 10, 0 to 8, or 0 to 6. In some embodiments, n is aninteger selected from 0 to 4. In some embodiments, n is 1, wherein saidat least one compound of Formula I, II, III, and V comprises the trimer.In some embodiments, n is greater than 1. In some embodiments, n is aninteger selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, and 20.

In certain embodiments, the compounds of Formula III may be largeroligomers or even polymeric in nature, wherein n is an integer selectedfrom 1 to 1,000, 1 to 750, 1 to 500 or 1 to 100. In certain embodiments,n is an integer equal to or greater than 50, 100, 250, or even 500. Incertain embodiments, n is an integer selected from 1 to 50 or 1 to 20.Without being bound to any particular theory, in certain embodiments, itis believed that compounds of Formula III have the ability to become“polymeric” in nature when they are prepared from terminally-unsaturatedfatty acids, wherein the linking of fatty acids at the terminal orpenultimate carbon of the fatty acid chain reduces branching and certainsteric hindrances typically observed in the oligomerization ofinternally-unsaturated fatty acids. In certain embodiments, thestability of the carbocation at the penultimate position of aterminally-unsaturated fatty acid will provide compounds of Formula IIIthat are linked predominantly at the penultimate carbon, such as theexemplary compound prepared in Scheme 1:

In certain embodiments, R₁ of Formula I, II, III, and V is an optionallysubstituted alkyl that is saturated or unsaturated, and branched orunbranched. In certain embodiments, the alkyl group is a C₁ to C₄₀alkyl, C₁ to C₂₂ alkyl or C₁ to C₁₈ alkyl. In some embodiments, thealkyl group is selected from C₇ to C₁₇ alkyl. In some embodiments, R₁ isselected from C₇ alkyl, C₉ alkyl, C₁₁ alkyl, C₁₃ alkyl, C₁₅ alkyl, andC₁₇ alkyl. In some embodiments, R₁ is selected from C₁₃ to C₁₇ alkyl,such as from C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments,R₁ is a C₁, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄,C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, or C₂₂ alkyl. In certain embodiments,R₁ is an optionally substituted, branched or unbranched alkyl having atleast one terminal site of unsaturation. In certain embodiments, R₁ isan optionally substituted, branched or unbranched alkyl having at leastone terminal site of unsaturation. In certain embodiments, R₁ is a C₂ toC₂₁ alkyl having at least one terminal site of unsaturation.

In certain embodiments, R₁ is selected from the structure of Formula IV:

-   -   wherein w is an integer selected from 0 to 13. In certain        embodiments, w is an integer selected from 5 to 7. In certain        embodiments, w is 7.

In some embodiments, R₂ of Formula I, II, III, and V is selected fromhydrogen and an optionally substituted alkyl that is saturated orunsaturated, and branched or unbranched. In some embodiments, the alkylgroup is a C₁ to C₄₀ alkyl, C₁ to C₂₂ alkyl or C₁ to C₁₋₈ alkyl. In someembodiments, the alkyl group is selected from C₇ to C₁₇ alkyl. In someembodiments, R₂ is selected from C₇ alkyl, C₉ alkyl, C₁₁ alkyl, C₁₃alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, R₂ is selectedfrom C₁₃ to C₁₇ alkyl, such as from C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl.In some embodiments, R₂ is a C₁, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀,C₁₁, C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, or C₂₂ alkyl.

In certain embodiments, R₃ and R₄, independently for each occurrence,are selected from optionally substituted alkyl that is saturated orunsaturated, and branched or unbranched. In some embodiments, the alkylgroup is a C₁ to C₄₀ alkyl, C₁ to C₂₂ alkyl or C₁ to C₁₈ alkyl. In someembodiments, the alkyl group is selected from C₇ to C₁₇ alkyl. In someembodiments, the alkyl group is selected from C₇ alkyl, C₉ alkyl, C₁₁alkyl, C₁₃ alkyl, C₁₅ alkyl, and C₁₇ alkyl. In some embodiments, thealkyl group is selected from C₁₃ to C₁₇ alkyl, such as from C₁₃ alkyl,C₁₅ alkyl, and C₁₇ alkyl.

In certain embodiments, R₃ and R₄, independently for each occurrence,are selected from

-   -   wherein R₃ and R₄ are independently optionally substituted and z        is, independently for each occurrence, an integer selected from        0 to 40.

In certain embodiments, one or more of R₃ or R₄ are unsubstituted. Incertain embodiments, z is, independently for each occurrence, an integerselected from 1 to 20. In certain embodiments, z is, independently foreach occurrence, an integer selected from 2 to 15. In certainembodiments, z is, independently for each occurrence, an integerselected from 5 to 7. In certain embodiments, z is, independently foreach occurrence, an integer selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. In certain embodiments, z is7.

As noted above, in certain embodiments, it may be possible to manipulateone or more of the compounds' properties by altering the length of R₁and/or its degree of saturation. However, in certain embodiments, thelevel of substitution on R₁ may also be altered to change or evenimprove the compounds' properties. Without being bound to any particulartheory, in certain embodiments, it is believed that the presence ofpolar substituents on R₁, such as one or more hydroxy groups, mayincrease the viscosity of the estolide, while increasing pour point.Accordingly, in some embodiments, R₁ will be unsubstituted or optionallysubstituted with a group that is not hydroxyl.

In some embodiments, the estolide is in its free-acid form, wherein R₂of Formula I, II, III, or V is hydrogen. In some embodiments, R₂ isselected from optionally substituted alkyl that is saturated orunsaturated, and branched or unbranched. In certain embodiments, the R₂residue may comprise any desired alkyl group, such as those derived fromesterification of the compound with the alcohols identified in theexamples herein. In some embodiments, the alkyl group is selected fromC₁ to C₄₀, C₁ to C₂₂, C₃ to C₂₀, C₁ to C₁₈, or C₆ to C₁₋₂ alkyl. In someembodiments, R₂ may be selected from C₃ alkyl, C₄ alkyl, C₈ alkyl, C₁₋₂alkyl, C₁₋₆ alkyl, C₁₋₈ alkyl, and C₂₀ alkyl. For example, in certainembodiments, R₂ may be branched, such as isopropyl, isobutyl, or2-ethylhexyl. In some embodiments, R₂ may be a larger alkyl group,branched or unbranched, comprising C₁₋₂ alkyl, C₁₋₆ alkyl, C₁₋₈ alkyl,or C₂₀ alkyl. Such groups at the R₂ position may be derived fromesterification of the free-acid compound using the Jarcol™ line ofalcohols marketed by Jarchem Industries, Inc. of Newark, N.J., includingJarcol™ I-18CG, 1-20, 1-12, 1-16, I-18T, and 85BJ. In some cases, R₂ maybe sourced from certain alcohols to provide branched alkyls such asisostearyl and isopalmityl. It should be understood that suchisopalmityl and isostearyl alkyl groups may cover any branched variationof C₁₆ and C₁₈, respectively. For example, the compounds describedherein may comprise highly-branched isopalmityl or isostearyl groups atthe R₂ position, derived from the Fineoxocol® line of isopalmityl andisostearyl alcohols marketed by Nissan Chemical America Corporation ofHouston, Tex., including Fineoxocol® 180, 180N, and 1600. Without beingbound to any particular theory, in embodiments, large, highly-branchedalkyl groups (e.g., isopalmityl and isostearyl) at the R₂ position ofthe estolides can provide at least one way to increase the lubricant'sviscosity, while substantially retaining or even reducing its pourpoint.

In some embodiments, the compounds described herein may comprise amixture of two or more compounds of Formula I, II, III, and V. It ispossible to characterize the chemical makeup of an estolide, a mixtureof estolides, or a composition comprising estolides, by using thecompound's, mixture's, or composition's measured estolide number (EN) ofcompound or composition. The EN represents the average number of fattyacids added to the base fatty acid. The EN also represents the averagenumber of estolide linkages per molecule:EN=n+1

wherein n is the number of secondary (β) fatty acids. Accordingly, asingle estolide compound will have an EN that is a whole number, forexample for dimers, trimers, and tetramers:dimer EN=1trimer EN=2tetramer EN=3

However, a composition comprising two or more estolide compounds mayhave an EN that is a whole number or a fraction of a whole number. Forexample, a composition having a 1:1 molar ratio of dimer and trimerwould have an EN of 1.5, while a composition having a 1:1 molar ratio oftetramer and trimer would have an EN of 2.5.

In some embodiments, the compositions may comprise a mixture of two ormore estolides having an EN that is an integer or fraction of an integerthat is greater than 4.5, or even 5.0. In some embodiments, the EN maybe an integer or fraction of an integer selected from about 1.0 to about5.0. In some embodiments, the EN is an integer or fraction of an integerselected from 1.2 to about 4.5. In some embodiments, the EN is selectedfrom a value greater than 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6,2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0, 5.2, 5.4,5.6 and 5.8. In some embodiments, the EN is selected from a value lessthan 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6,3.8, 4.0, 4.2, 4.4, 4.6, 4.8, and 5.0, 5.2, 5.4, 5.6, 5.8, and 6.0. Insome embodiments, the EN is selected from 1, 1.2, 1.4, 1.6, 1.8, 2.0,2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8,5.0, 5.2, 5.4, 5.6, 5.8, and 6.0.

As noted above, it should be understood that the chains of the estolidecompounds may be independently optionally substituted, wherein one ormore hydrogens are removed and replaced with one or more of thesubstituents identified herein. Similarly, two or more of the hydrogenresidues may be removed to provide one or more sites of unsaturation,such as a cis or trans double bond. Further, the chains may optionallycomprise branched hydrocarbon residues. For example, in some embodimentsthe estolides described herein may comprise at least one compound ofFormula II:

wherein

m is an integer equal to or greater than 1;

n is an integer equal to or greater than 0;

R₁, independently for each occurrence, is an optionally substitutedalkyl that is saturated or unsaturated, and branched or unbranched;

R₂ is selected from hydrogen and optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched; and

R₃ and R₄, independently for each occurrence, are selected fromoptionally substituted alkyl that is saturated or unsaturated, andbranched or unbranched,

wherein at least one of R₁, R₃, and R₄ comprises an unbranched undecanylthat is saturated or unsaturated.

In certain embodiments, m is 1. In some embodiments, m is an integerselected from 2, 3, 4, and 5. In some embodiments, n is an integerselected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12. In someembodiments, one or more R₃ differs from one or more other R₃ in acompound of Formula II. In some embodiments, one or more R₃ differs fromR₄ in a compound of Formula II. In some embodiments, if the compounds ofFormula II are prepared from one or more polyunsaturated fatty acids, itis possible that one or more of R₃ and R₄ will have one or more sites ofunsaturation. In some embodiments, if the compounds of Formula II areprepared from one or more branched fatty acids, it is possible that oneor more of R₃ and R₄ will be branched.

In some embodiments, R₃ and R₄ can be CH₃(CH₂)_(y)CH(CH₂)_(x)—, where xis, independently for each occurrence, an integer selected from 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20, andy is, independently for each occurrence, an integer selected from 0, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.Where both R₃ and R₄ are CH₃(CH₂)_(y)CH(CH₂)_(x)—, the compounds may becompounds according to Formula I and V.

In certain embodiments, the compounds described herein may comprise atleast one compound of Formula III:

wherein

n is an integer equal to or greater than 0;

R₁ is an optionally substituted, branched or unbranched alkyl that issaturated or unsaturated;

R₂ is selected from hydrogen and optionally substituted alkyl that issaturated or unsaturated, and branched or unbranched; and

R₃ and R₄, independently for each occurrence, are selected from

wherein R₃ and R₄ are independently optionally substituted and z is,independently for each occurrence, an integer selected from 0 to 40.

In certain embodiments, compounds of Formula III may comprise largeroligomers and, in some cases, may be considered polymeric in nature,wherein n is an integer greater than 0, such as greater than 10, 15, 20,30, or even 50. In certain embodiments, compounds of Formula III areprepared by linking two or more fatty acids having at least one terminalsite of unsaturation, wherein a covalent bond is formed between anoxygen of a carboxylic group of a first fatty acid and a carbon of aterminal site of unsaturation of a second fatty acid.

Without being bound to any particular theory, in certain embodiments,altering the EN produces estolides having desired viscometric propertieswhile substantially retaining or even reducing pour point. For example,in some embodiments the estolides exhibit a decreased pour point uponincreasing the EN value. Accordingly, in certain embodiments, a methodis provided for retaining or decreasing the pour point of an estolidebase oil by increasing the EN of the base oil, or a method is providedfor retaining or decreasing the pour point of a composition comprisingan estolide base oil by increasing the EN of the base oil. In someembodiments, the method comprises: selecting an estolide base oil havingan initial EN and an initial pour point; and removing at least a portionof the base oil, said portion exhibiting an EN that is less than theinitial EN of the base oil, wherein the resulting estolide base oilexhibits an EN that is greater than the initial EN of the base oil, anda pour point that is equal to or lower than the initial pour point ofthe base oil. In some embodiments, the selected estolide base oil isprepared by oligomerizing at least one first unsaturated fatty acid withat least one second unsaturated fatty acid and/or saturated fatty acid.In some embodiments, the removing at least a portion of the base oil isaccomplished by distillation, chromatography, membrane separation, phaseseparation, affinity separation, solvent extraction, or combinationsthereof. In some embodiments, the distillation takes place at atemperature and/or pressure that is suitable to separate the estolidebase oil into different “cuts” that individually exhibit different ENvalues. In some embodiments, this may be accomplished by subjecting thebase oil temperature of at least about 250° C. and an absolute pressureof no greater than about 25 microns. In some embodiments, thedistillation takes place at a temperature range of about 250° C. toabout 310° C. and an absolute pressure range of about 10 microns toabout 25 microns.

In some embodiments, the compounds and compositions exhibit an EN thatis greater than or equal to 1, such as an integer or fraction of aninteger selected from about 1.0 to about 2.0. In some embodiments, theEN is an integer or fraction of an integer selected from about 1.0 toabout 1.6. In some embodiments, the EN is a fraction of an integerselected from about 1.1 to about 1.5. In some embodiments, the EN isselected from a value greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6,1.7, 1.8, and 1.9. In some embodiments, the EN is selected from a valueless than 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0.

In some embodiments, the EN is greater than or equal to 1.5, such as aninteger or fraction of an integer selected from about 1.8 to about 2.8.In some embodiments, the EN is an integer or fraction of an integerselected from about 2.0 to about 2.6. In some embodiments, the EN is afraction of an integer selected from about 2.1 to about 2.5. In someembodiments, the EN is selected from a value greater than 1.8, 1.9, 2.0,2.1, 2.2, 2.3, 2.4, 2.5, 2.6, and 2.7. In some embodiments, the EN isselected from a value less than 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6,2.7, and 2.8. In some embodiments, the EN is about 1.8, 2.0, 2.2, 2.4,2.6, or 2.8.

In some embodiments, the EN is greater than or equal to about 4, such asan integer or fraction of an integer selected from about 4.0 to about5.0. In some embodiments, the EN is a fraction of an integer selectedfrom about 4.2 to about 4.8. In some embodiments, the EN is a fractionof an integer selected from about 4.3 to about 4.7. In some embodiments,the EN is selected from a value greater than 4.0, 4.1, 4.2, 4.3, 4.4,4.5, 4.6, 4.7, 4.8, and 4.9. In some embodiments, the EN is selectedfrom a value less than 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, and5.0. In some embodiments, the EN is about 4.0, 4.2, 4.4, 4.6, 4.8, or5.0.

In some embodiments, the EN is greater than or equal to about 5, such asan integer or fraction of an integer selected from about 5.0 to about6.0. In some embodiments, the EN is a fraction of an integer selectedfrom about 5.2 to about 5.8. In some embodiments, the EN is a fractionof an integer selected from about 5.3 to about 5.7. In some embodiments,the EN is selected from a value greater than 5.0, 5.1, 5.2, 5.3, 5.4,5.5, 5.6, 5.7, 5.8, and 5.9. In some embodiments, the EN is selectedfrom a value less than 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, and6.0. In some embodiments, the EN is about 5.0, 5.2, 5.4, 5.4, 5.6, 5.8,or 6.0.

In some embodiments, the EN is greater than or equal to 1, such as aninteger or fraction of an integer selected from about 1.0 to about 2.0.In some embodiments, the EN is a fraction of an integer selected fromabout 1.1 to about 1.7. In some embodiments, the EN is a fraction of aninteger selected from about 1.1 to about 1.5. In some embodiments, theEN is selected from a value greater than 1.0, 1.1, 1.2, 1.3, 1.4, 1.5,1.6, 1.7, 1.8, or 1.9. In some embodiments, the EN is selected from avalue less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. In someembodiments, the EN is about 1.0, 1.2, 1.4, 1.6, 1.8, or 2.0. In someembodiments, the EN is greater than or equal to 1, such as an integer orfraction of an integer selected from about 1.2 to about 2.2. In someembodiments, the EN is an integer or fraction of an integer selectedfrom about 1.4 to about 2.0. In some embodiments, the EN is a fractionof an integer selected from about 1.5 to about 1.9. In some embodiments,the EN is selected from a value greater than 1.0, 1.1. 1.2, 1.3, 1.4,1.5, 1.6, 1.7, 1.8, 1.9, 2.0, and 2.1. In some embodiments, the EN isselected from a value less than 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9,2.0, 2.1, and 2.2. In some embodiments, the EN is about 1.0, 1.2, 1.4,1.6, 1.8, 2.0, or 2.2.

In some embodiments, the EN is greater than or equal to 2, such as aninteger or fraction of an integer selected from about 2.8 to about 3.8.In some embodiments, the EN is an integer or fraction of an integerselected from about 2.9 to about 3.5. In some embodiments, the EN is aninteger or fraction of an integer selected from about 3.0 to about 3.4.In some embodiments, the EN is selected from a value greater than 2.0,2.1, 2.2, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.4, 3.5, 3.6, and3.7. In some embodiments, the EN is selected from a value less than 2.2,2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6,3.7, and 3.8. In some embodiments, the EN is about 2.0, 2.2, 2.4, 2.6,2.8, 3.0, 3.2, 3.4, 3.6, or 3.8. Typically, base stocks and lubricantcompositions exhibit certain lubricity, viscosity, and/or pour pointcharacteristics. For example, in certain embodiments, suitable viscositycharacteristics of the base oil may range from about 10 cSt to about 250cSt at 40° C., and/or about 3 cSt to about 30 cSt at 100° C. In someembodiments, the compounds and compositions may exhibit viscositieswithin a range from about 50 cSt to about 150 cSt at 40° C., and/orabout 10 cSt to about 20 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 55 cSt at 40° C. or less than about 45 cStat 40° C., and/or less than about 12 cSt at 100° C. or less than about10 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit viscosities within a range from about 25 cSt toabout 55 cSt at 40° C., and/or about 5 cSt to about 11 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 35 cSt to about 45 cSt at 40° C.,and/or about 6 cSt to about 10 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 38 cSt to about 43 cSt at 40° C., and/or about 7 cSt toabout 9 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 120 cSt at 40° C. or less than about 100 cStat 40° C., and/or less than about 18 cSt at 100° C. or less than about17 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 70 cSt toabout 120 cSt at 40° C., and/or about 12 cSt to about 18 cSt at 100° C.In some embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 80 cSt to about 100 cSt at 40° C.,and/or about 13 cSt to about 17 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 85 cSt to about 95 cSt at 40° C., and/or about 14 cStto about 16 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities greater than about 180 cSt at 40° C. or greater than about200 cSt at 40° C., and/or greater than about 20 cSt at 100° C. orgreater than about 25 cSt at 100° C. In some embodiments, the estolidecompounds and compositions may exhibit a viscosity within a range fromabout 180 cSt to about 230 cSt at 40° C., and/or about 25 cSt to about31 cSt at 100° C. In some embodiments, estolide compounds andcompositions may exhibit viscosities within a range from about 200 cStto about 250 cSt at 40° C., and/or about 25 cSt to about 35 cSt at 100°C. In some embodiments, estolide compounds and compositions may exhibitviscosities within a range from about 210 cSt to about 230 cSt at 40°C., and/or about 28 cSt to about 33 cSt at 100° C. In some embodiments,the estolide compounds and compositions may exhibit viscosities within arange from about 200 cSt to about 220 cSt at 40° C., and/or about 26 cStto about 30 cSt at 100° C. In some embodiments, the estolide compoundsand compositions may exhibit viscosities within a range from about 205cSt to about 215 cSt at 40° C., and/or about 27 cSt to about 29 cSt at100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 45 cSt at 40° C. or less than about 38 cStat 40° C., and/or less than about 10 cSt at 100° C. or less than about 9cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 20 cSt toabout 45 cSt at 40° C., and/or about 4 cSt to about 10 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 28 cSt to about 38 cSt at 40° C.,and/or about 5 cSt to about 9 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 30 cSt to about 35 cSt at 40° C., and/or about 6 cSt toabout 8 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities less than about 80 cSt at 40° C. or less than about 70 cStat 40° C., and/or less than about 14 cSt at 100° C. or less than about13 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit a viscosity within a range from about 50 cSt toabout 80 cSt at 40° C., and/or about 8 cSt to about 14 cSt at 100° C. Insome embodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 60 cSt to about 70 cSt at 40° C.,and/or about 9 cSt to about 13 cSt at 100° C. In some embodiments, theestolide compounds and compositions may exhibit viscosities within arange from about 63 cSt to about 68 cSt at 40° C., and/or about 10 cStto about 12 cSt at 100° C.

In some embodiments, the estolide compounds and compositions may exhibitviscosities greater than about 120 cSt at 40° C. or greater than about130 cSt at 40° C., and/or greater than about 15 cSt at 100° C. orgreater than about 18 cSt at 100° C. In some embodiments, the estolidecompounds and compositions may exhibit a viscosity within a range fromabout 120 cSt to about 150 cSt at 40° C., and/or about 16 cSt to about24 cSt at 100° C. In some embodiments, the estolide compounds andcompositions may exhibit viscosities within a range from about 130 cStto about 160 cSt at 40° C., and/or about 17 cSt to about 28 cSt at 100°C. In some embodiments, the estolide compounds and compositions mayexhibit viscosities within a range from about 130 cSt to about 145 cStat 40° C., and/or about 17 cSt to about 23 cSt at 100° C. In someembodiments, the estolide compounds and compositions may exhibitviscosities within a range from about 135 cSt to about 140 cSt at 40°C., and/or about 19 cSt to about 21 cSt at 100° C. In some embodiments,the estolide compounds and compositions may exhibit viscosities of about1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20,21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 32, 34, 36, 38, 40, 42, 44, 46,48, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140,150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280,290, 300, 350, or 400 cSt. at 40° C. In some embodiments, the estolidecompounds and compositions may exhibit viscosities of about 1, 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,24, 25, 26, 27, 28, 29, and 30 cSt at 100° C. In certain embodiments,estolides may exhibit desirable low-temperature pour point properties.In some embodiments, the estolide compounds and compositions may exhibita pour point lower than about −25° C., about −35° C., −40° C., or evenabout −50° C. In some embodiments, the estolide compounds andcompositions have a pour point of about −25° C. to about −45° C. In someembodiments, the pour point falls within a range of about −30° C. toabout −40° C., about −34° C. to about −38° C., about −30° C. to about−45° C., −35° C. to about −45° C., 34° C. to about −42° C., about −38°C. to about −42° C., or about 36° C. to about −40° C. In someembodiments, the pour point falls within the range of about −27° C. toabout −37° C., or about −30° C. to about −34° C. In some embodiments,the pour point falls within the range of about −25° C. to about −35° C.,or about −28° C. to about −32° C. In some embodiments, the pour pointfalls within the range of about −28° C. to about −38° C., or about −31°C. to about −35° C. In some embodiments, the pour point falls within therange of about −31° C. to about −41° C., or about −34° C. to about −38°C. In some embodiments, the pour point falls within the range of about−40° C. to about −50° C., or about −42° C. to about −48° C. In someembodiments, the pour point falls within the range of about −50° C. toabout −60° C., or about −52° C. to about −58° C. In some embodiments,the upper bound of the pour point is less than about −35° C., about −36°C., about −37° C., about −38° C., about −39° C., about −40° C., about−41° C., about −42° C., about −43° C., about −44° C., or about −45° C.In some embodiments, the lower bound of the pour point is greater thanabout −70° C., about −69° C., about −68° C., about −67° C., about −66°C., about −65° C., about −64° C., about −63° C., about −62° C., about−61° C., about −60° C., about −59° C., about −58° C., about −57° C.,about −56° C., −55° C., about −54° C., about −53° C., about −52° C.,−51, about −50° C., about −49° C., about −48° C., about −47° C., about−46° C., or about −45° C.

In addition, in certain embodiments, the compounds may exhibit decreasedIodine Values (IV) when compared to compounds prepared by other methods.IV is a measure of the degree of total unsaturation of an oil, and isdetermined by measuring the amount of iodine per gram of estolide(cg/g). In certain instances, oils having a higher degree ofunsaturation may be more susceptible to creating corrosiveness anddeposits, and may exhibit lower levels of oxidative stability. Compoundshaving a higher degree of unsaturation will have more points ofunsaturation for iodine to react with, resulting in a higher IV. Thus,in certain embodiments, it may be desirable to reduce the IV of thecompounds in an effort to increase the compound's oxidative stability,while also decreasing harmful deposits and the corrosiveness of thecompound.

In some embodiments, compounds and compositions described herein have anIV of less than about 40 cg/g or less than about 35 cg/g. In someembodiments, the compounds have an IV of less than about 30 cg/g, lessthan about 25 cg/g, less than about 20 cg/g, less than about 15 cg/g,less than about 10 cg/g, or less than about 5 cg/g. The IV of acomposition may be reduced by decreasing the compound's degree ofunsaturation. This may be accomplished by, for example, by increasingthe amount of saturated capping materials relative to unsaturatedcapping materials when synthesizing the compounds. Alternatively, incertain embodiments, IV may be reduced by hydrogenating compounds havingunsaturated caps.

In certain embodiments, the estolides described herein may be preparedfrom non-naturally occurring fatty acid starting materials. In certainembodiments, the fatty acid starting materials may be derived throughthe cross metathesis of naturally-occurring fatty acid residues. Incertain embodiments, the estolides are prepared through the processcomprising:

providing at least one fatty acid substrate;

providing at least one alpha olefin;

contacting the at least one fatty acid substrate with the at least onealpha olefin in the presence of a metathesis catalyst to provide anolefin product and a metathesized fatty acid product;

optionally converting the metathesized fatty acid product into at leastone first fatty acid product;

optionally providing at least one second fatty acid reactant;

providing an oligomerization catalyst; and

oligomerizing the metathesized fatty acid product and/or first fattyacid product, optionally with the at least one second fatty acidreactant, in the presence of the oligomerization catalyst to produce anestolide base oil.

In certain embodiments, the fatty acid substrate is a compound orcomposition comprising at least one fatty acid residue. In certainembodiments, the fatty acid substrate comprises at least one internalsite of unsaturation, wherein said site of unsaturation is not at theterminus (i.e., alpha position) of the at least one of the fatty acidresidue of said fatty acid substrate. In certain embodiments, the atleast one site of unsaturation is a double bond, such as the double bondat the 9 position of oleic acid, the double bonds at the 9 and 12position of linoleic acid, or the double bonds at the 9, 12, and 15positions of linolenic acid. In certain embodiments, the at least onefatty acid substrate is selected from unsaturated fatty acids,unsaturated fatty acid esters (e.g., alkyl esters and glycerides), andunsaturated fatty acid oligomers. In certain embodiments, the at leastone fatty acid substrate is selected from monoglycerides, diglycerides,and triglycerides. In certain embodiments, the at least one fatty acidsubstrate comprises one or more fatty acids or fatty acid alkyl estersderived from monoglycerides, diglycerides, or triglycerides viahydrolysis and transesterification, respectively.

In certain embodiments, the at least one fatty acid substrate iscontacted with at least one alpha olefin in the presence of a metathesiscatalyst to provide an olefin product and a metathesized fatty acidproduct. In certain embodiments, the olefin product is a terminal olefinand/or an internal olefin. For example, a fatty acid triglyceridecomprising an oleic acid residue may be contacted with an alpha olefinsuch as 1-butene in the presence of a metathesis catalyst to provide,inter alia, a metathesized fatty acid product (triglyceride comprising a9-dodecenoic acid residue) and a terminal olefin (1-decene), as shown inScheme 2:

In certain embodiments, the resulting metathesized fatty acid product(s)is converted into at least one first fatty acid product. For example, itmay be desirable to convert the triglyceride comprising a 9-dodecenoicacid residue (metathesized fatty acid product) into 9-dodecenoic acid(first fatty acid product) by subjecting the triglyceride to hydrolysisconditions, as shown in Scheme 3:

Alternatively, it may be desirable to convert the triglyceridecomprising a 9-dodecenoic acid residue (metathesized fatty acid product)into a 9-dodecenoic acid ester (first fatty acid product) by subjectingthe triglyceride to transesterification conditions in the presence of analcohol (e.g., methanol). Exemplary processes include the one set forthin Scheme 4:

Suitable hydrolysis and transesterification conditions include any ofthe methods known to persons of ordinary skill in the art, such asacid-catalyzed and/or Lewis Acid-catalyzed conditions. In certainembodiments, the at least one fatty acid substrate will comprise a freefatty acid, which may be reacted with an alpha olefin to provide ametathesized fatty acid product that is also a free fatty acid. Thus, incertain embodiments, the optional converting of the metathesized fattyacid product into at least one first fatty acid product is notundertaken.

In certain embodiments, the at least one fatty acid substrate may bereacted with at least one alpha olefin, such as alpha olefincross-metathesis compound. In certain embodiments, the at least onealpha olefin may comprise more than 2 carbons, such as from 2 to 20carbons. In certain embodiments, the at least one fatty acid substrateis reacted with ethene to provide a metathesized fatty acid producthaving a fatty acid residue with at least one terminal site ofunsaturation. In certain embodiments, the alpha olefin comprises 3 ormore carbons, such as from 3 to 10 carbons. In certain embodiments,reacting the at least one fatty acid substrate with an alpha olefincomprising 3 or more carbons provides a metathesized fatty acid productcomprising at least one internal site of unsaturation.

Exemplary alpha olefins include, but are not limited to, ethene,propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene,1-eicosene and larger alpha olefins, 2-propenol, 3-butenol, 4-pentenol,5-hexenol, 6-heptenol, 7-octenol, 8-nonenol, 9-decenol, 10-undecenol,11-dodecenol, 12-tridecenol, 13-tetradecenol, 14-pentadecenol,15-hexadecenol, 16-heptadecenol, 17-octadecenol, 18-nonadecenol,19-eicosenol and larger alpha alkenols, 2-propenyl acetate, 3-butenylacetate, 4-pentenyl acetate, 5-hexenyl acetate, 6-heptenyl acetate,7-octenyl acetate, 8-nonenyl acetate, 9-decenyl acetate, 10-undecenylacetate, 11-dodecenyl acetate, 12-tridecenyl acetate 13-tetradecenylacetate, 14-pentadecenyl acetate, 15-hexadecenyl acetate,16-heptadecenyl acetate, 17-octadecenyl acetate, 18-nonadecenyl acetate,19-eicosenyl acetate and larger alpha-alkenyl acetates, 2-propenylchloride, 3-butenyl chloride, 4-pentenyl chloride, 5-hexenyl chloride,6-heptenyl chloride, 7-octenyl chloride, 8-nonenyl chloride, 9-decenylchloride, 10-undecenyl chloride, 11-dodecenyl chloride, 12-tridecenylchloride, 13-tetradecenyl chloride, 14-pentadecenyl chloride,15-hexadecenyl chloride, 16-heptadecenyl chloride, 17-octadecenylchloride, 18-nonadecenyl chloride, 19-eicosenyl chloride and largeralpha-alkenyl chlorides, bromides, and iodides, allyl cyclohexane, allylcyclopentane, and the like. Exemplary disubstituted alpha-olefinsinclude, but are not limited to, isobutylene, 2-methylbut-1-ene,2-methylpent-1-ene, 2-methylhex-1-ene, 2-methylhept-1-ene,2-methyloct-1-ene, and the like.

In certain embodiments, the at least one alpha olefin is selected frompropene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. Incertain embodiments, the at least one first fatty acid substrate isreacted with at least one alpha olefin having 3 or more carbons toprovide a metathesized fatty acid product having a fatty acid residuewith at least one internal site of unsaturation.

In certain embodiments, the reactions described comprise reactioncomponents that include at least one fatty acid substrate and at leastone alpha olefin. In certain embodiments, the reaction components may besolid, liquid, or gaseous. In certain embodiments, the reaction can becarried out under conditions to ensure the at least one fatty acidsubstrate and the at least one alpha olefin are liquid. In certainembodiments, the use of a liquid cross-metathesis partner instead of agaseous alpha olefin (e.g., ethylene) may allow for the convenientcontrolling of reaction pressures, and may reduce or eliminate the needfor vapor condensers and vapor reclaiming equipment.

In certain embodiments, the at least one alpha olefin is soluble in theat least one fatty acid substrate. In certain embodiments, the at leastone alpha olefin may have a solubility of at least 0.25 M, at least 1 M,at least 3 M, or at least 5 M in the at least one fatty acid substrate.In certain embodiments, the at least one alpha olefin has a lowsolubility in the at least one fatty acid substrate, and thecross-metathesis reaction occurs as an interfacial reaction. In certainembodiments, the at least one alpha olefin may be provided in the formof a gas. In certain embodiments, the pressure of a gaseous alpha olefinover the reaction solution is maintained in a range that has a minimumof about 10 psig, 15 psig, 50 psig, or 80 psig, and a maximum of about250 psig, 200 psig, 150 psig, or 130 psig.

In certain embodiments, the metathesis reaction is catalyzed by anysuitable cross-metathesis catalysts known to persons of skill in theart. In certain embodiments, the catalyst is added to the reactionmedium as a solid, but may also be added as a solution wherein thecatalyst is dissolved in an appropriate solvent. In certain embodiments,the catalyst loading will depend on a variety of factors such as theidentity of the reactants and the reaction conditions that are employed.In certain embodiments, the catalyst will be present in an amount thatranges from about 0.1 ppm, 1 ppm, or 5 ppm, to about 10 ppm, 15 ppm, 25ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relative to theamount of the at least one fatty acid substrate. Catalyst loading, whenmeasured in ppm relative to the amount of the at least one fatty acidsubstrate, may be calculated using the equation

${{ppm}\mspace{14mu}{catalyst}} = {\frac{{moles}\mspace{14mu}{catalyst}}{\begin{matrix}{{moles}\mspace{14mu}{fatty}\mspace{14mu}{acid}} \\{{substrate}\mspace{14mu}{double}\mspace{14mu}{bonds}}\end{matrix}}*1\text{,}000\text{,}000}$In certain embodiments, the amount of catalyst is measured in terms ofmol % relative to the amount of the at least one fatty acid substrate,using the equation

${{mol}\mspace{14mu}\%\mspace{14mu}{catalyst}} = {\frac{{moles}\mspace{14mu}{catalyst}}{{moles}\mspace{14mu}{fatty}\mspace{14mu}{acid}\mspace{14mu}{substrate}\mspace{14mu}{double}\mspace{14mu}{bonds}}*100}$Thus, in certain embodiments, the metathesis catalyst is present in anamount that ranges from about 0.00001 mol %, 0.0001 mol %, or 0.0005 mol%, to about 0.001 mol %, 0.0015 mol %, 0.0025 mol %, 0.005 mol %, 0.01mol %, 0.02 mol %, 0.05 mol %, or 0.1 mol % relative to the at least onefatty acid substrate.

In certain embodiments, the cross metathesis is carried out under a dry,inert atmosphere. Such an atmosphere may be created using any inert gas,including such gases as nitrogen and argon. In certain embodiments, theuse of an inert atmosphere may be optimal in terms of promoting catalystactivity, and reactions performed under an inert atmosphere may beperformed with relatively low catalyst loading. In certain embodiments,the reactions of the may also be carried out in an oxygen-containingand/or a water-containing atmosphere, and in certain embodiments, thereactions are carried out under ambient conditions. In certainembodiments, the presence of oxygen, water, or other impurities in thereaction may necessitate the use of higher catalyst loadings as comparedwith reactions performed under an inert atmosphere.

In certain embodiments, the metathesis catalyst comprises one or morecompounds selected from alkylidene methathesis catalysts, such as osmiumand ruthenium alkylidene catalysts. In certain embodiments, themetathesis catalyst is selected from one or more compounds of Formula A:

wherein

M is a Group 8 transition metal;

L¹, L² and L³ are independently selected from optionally substitutedalkyl, optionally substituted aryl, optionally substituted heteroaryl(e.g., imidazole, pyrazine, pyridine, pyrrole), optionally substitutedheterocycloalkyl (e.g., imidazolidine, pyrazolidine), phosphine,sulfonated phosphine, phosphite, phosphonite, arsine, optionallysubstituted amine, sulfoxide, nitrosyl, and thioether;

n is 0 or 1;

m is 0, 1 or 2;

X¹ and X² are independently selected from hydrogen, halogen (e.g.,chlorine), optionally substituted alkyl, optionally substituted alkoxy,optionally substituted aryl, optionally substituted heteroaryl,optionally substituted heterocycloalkyl; and

R¹ and R² are independently selected from hydrogen and optionallysubstituted alkyl, optionally substituted aryl, optionally substitutedheteroaryl, and optionally substituted heterocycloalkyl, wherein any twoor more of X¹, X², L¹, L², L³, R¹ and R² can optionally taken togetherto form a cyclic or heterocyclic group, and wherein further any one ormore of X¹, X², L¹, L², L³, R¹ and R² may be attached to a support.

Exemplary metathesis catalysts include, but are not limited to,alkylidene catalysts generally known as first and second generationGrubbs' catalysts. Other exemplary catalysts and methods of making thesame may include those described in Schwab et al. (1996) J. Am. Chem.Soc. 118:100-110; Scholl et al. (1999) Org. Lett. 6:953-956; Sanford etal. (2001) J. Am. Chem. Soc. 123:749-750; U.S. Pat. No. 5,312,940; U.S.Pat. No. 5,342,909; U.S. Patent Publication No. 2003/0055262 to Grubbset al. filed Apr. 16, 2002; International Patent Publication No. WO02/079208; International Patent Publication No. WO 03/11455A1 to Grubbset al. published Feb. 13, 2003, all of which are incorporated byreference in their entireties for all purposes.

As described above, the at least one fatty acid substrate can bemetathesized to provide a metathesized fatty acid product. In certainembodiments, the metathesis leaves the fatty acid substratesubstantially intact and/or unchanged, but for the cleavage andshortening of the at least one fatty acid residue of said fatty acidsubstrate. For example, in certain embodiments, the metathesis of adiglyceride comprising an oleic acid residue with 1-butene will providea diglyceride comprising a 9-dodecenoic acid residue, as well as acleaved 1-decene terminal olefin. In certain embodiments, the crossmetathesis of the at least one fatty acid substrate provides a mixtureof multiple products. For example, the cross metathesis of the methylester of oleic acid may provide a mixture of 1-decene, 3-dodecene,9-dodecenoic acid methyl ester, and 9-decenoic acid methyl ester.

In certain embodiments, the metathesized fatty acid product and/or firstfatty acid product are independently selected from unsaturated fattyacids, unsaturated fatty acid esters, and unsaturated fatty acidoligomers. In some embodiments, the at least one second fatty acidreactant is selected from saturated and unsaturated fatty acids andsaturated and unsaturated fatty acid oligomers.

In certain embodiments, the process of producing an estolide base oilcomprises oligomerizing the at least one second fatty acid reactant withthe metathesized fatty acid product and/or fatty acid product in thepresence of an oligomerization catalyst. In certain embodiments, theprocess comprises the oligomerization of one or more free fatty acids.

In certain embodiments, when the at least one first fatty acid substratecomprises an unsaturated free fatty acid, the resulting metathesizedfatty acid product is also a free fatty acid and is not converted intoat least one first fatty acid product. Thus, in certain embodiments, themetathesized fatty acid product is oligomerized to provide an estolidebase oil. In certain embodiments, the metathesized fatty acid productmay be oligomerized with at least one second fatty acid reactant.

In certain embodiments, the oligomerizing of the metathesized fatty acidproduct and/or first fatty acid product, optionally with the at leastone second fatty acid reactant, will result in the production of a freefatty acid oligomer. For example, metathesis of at least one first fattyacid substrate that comprises an oleic acid residue-containingtriglyceride will result in a 9-dodecenoic acid residue-containingtriglyceride metathesized fatty acid product. Hydrolysis of thatmetathesized fatty acid product will result in 9-dodecenoic acid (firstfatty acid product), which can subsequently be oligomerized by itselfand/or with at least one second fatty acid reactant (e.g., oleic acid,9-decenoic acid) to provide a free fatty acid oligomer (estolide baseoil). Alternatively, transesterification of the metathesized fatty acidproduct with an alcohol will provide a 9-dodecenoic acid ester (firstfatty acid product), which can subsequently be contacted with at leastone second fatty acid reactant (e.g., oleic acid, 9-dodecenoic acid) toprovide the esterified estolide. In certain embodiments, when the firstfatty acid product is an ester, the resulting esterified estolide willexist predominantly in its dimer form (isomers possible). Exemplaryprocesses include those set forth in Scheme 5:

In certain embodiments, the resulting estolide base oil is in itsfree-acid form, wherein the base fatty acid residue is unesterified(e.g., R₂ is hydrogen for compounds of Formula I). Accordingly, incertain embodiments, the process further comprises esterifying theestolide base oil with an alcohol to provide an esterified estolide baseoil. Exemplary esterification methods include those set forth below inScheme 9.

In certain embodiments, the process of producing the estolide base oilcomprises

providing at least one fatty acid substrate having at least one fattyacid residue with at least one internal site of unsaturation;

providing at least one alpha olefin;

contacting the at least one fatty acid substrate with the at least onealpha olefin in the presence of a metathesis catalyst to provide anolefin product and a metathesized fatty acid product;

optionally providing at least one second fatty acid reactant;

providing an oligomerization catalyst; and

oligomerizing the metathesized fatty acid product, optionally with theat least one second fatty acid reactant, in the presence of theoligomerization catalyst to produce an estolide base oil

In certain embodiments, the at least one fatty acid substrate, at leastone alpha olefin, metathesis catalyst, metathesized fatty acid product,oligomerization catalyst, and the optional at least one second fattyacid reactant may comprise any of the compounds and compositionspreviously described herein. In certain embodiments, the at least onefirst fatty acid substrate is selected from unsaturated fatty acids andunsaturated fatty acid esters. In certain embodiments, the at least onealpha olefin is selected from ethylene, propene, 1-butene, 1-pentene,1-hexene, 1-heptene, and 1-octene. In certain embodiments, themetathesis catalyst is an osmium or ruthenium alkylidene metathesiscatalyst.

In certain embodiments, the at least one fatty acid substrate comprisesat least one fatty acid residue selected from oleic acid, linoleic acid,and linolenic acid. In certain embodiments, the at least one fatty acidsubstrate is an unsaturated fatty acid. In certain embodiments, themetathesized fatty acid product comprises an unsaturated fatty acid. Incertain embodiments, the metathesized fatty acid product comprises amixture of a fatty acid having a terminal site of unsaturation (e.g.,9-decenoic acid) and a fatty acid having an internal site ofunsaturation (e.g., 9-dodecenoic acid). In certain embodiments, theolefin product comprises a mixture of a terminal olefin (e.g., 1-decene)and an internal olefin (e.g., 3-dodecene). In certain embodiments, themetathesized fatty acid product is a terminal fatty acid such as9-decenoic acid, and the at least one internal olefin such as3-dodecene. In certain embodiments, the metathesized fatty acid productis a terminal fatty acid such as 9-decenoic acid, and the olefin productis a terminal olefin such as 1-decene. An exemplary process includes theone set forth in Scheme 6:

In certain embodiments, the resulting estolide base oil is in itsfree-acid form, wherein the base fatty acid residue is unesterified(e.g., R₂ is hydrogen for compounds of Formula III). Accordingly, incertain embodiments, the process further comprises esterifying theestolide base oil with an alcohol to provide an esterified estolide baseoil.

In certain embodiments, the estolides described herein may be preparedfrom naturally occurring fatty acid starting materials. However, incertain embodiments, it may be desirable to alter the structure of theestolide in an effort to improve its properties. As noted above, incertain embodiments, estolides comprises shorter fatty acid caps mayprovide desirable cold-temperature properties. Accordingly, in certainembodiments, the process for producing the estolide comprises:

-   -   providing at least one estolide compound having at least one        fatty acid chain residue with at least one internal site of        unsaturation;    -   providing at least one alpha olefin; and    -   contacting the at least one estolide compound with the at least        one alpha olefin in the presence of a metathesis catalyst to        provide an olefin product and an estolide base oil, wherein said        estolide base oil comprises at least one fatty acid chain        residue with at least one terminal site of unsaturation or at        least one internal site of unsaturation.

In certain embodiments, the at least one estolide compound is preparedby any of the processes described herein, such as the oligomerization ofoleic acid. In certain embodiments, the resulting at least one estolidecompound will comprise at least one fatty acid residue having at leastone internal site of unsaturation. For example, the oligomerization ofoleic acid molecules will result in an estolide having an oleic-acid(oleate) cap. In certain embodiments, it may be desirable to remove theinternal site of unsaturation by subjecting the at least one estolidecompound to cross metathesis conditions, wherein the resulting oleicestolide comprises a truncated alkyl cap (i.e., C₁₀ alkyl) having aterminal double bond. However, depending on the manner in which theestolide compound is prepared, it is possible that the at least oneestolide compound will have internal sites of unsaturation on fatty acidresidues that are not the capping group. For example, preparingestolides with a mixture of fatty acid reactants that includespolyunsaturates may result in compounds having internal sites ofunsaturation on the base fatty acid residue, or even on one or more ofthe linking residues. In certain embodiments, subjecting such estolidecompounds to cross metathesis conditions will result in estolide baseoils having truncated linking and/or base fatty acid residues with atleast one terminal site of unsaturation. In certain embodiments, thisprocess provides a method for preparing compounds of Formula V.

In certain embodiments, the at least one estolide compound having atleast one fatty acid chain residue with at least one internal site ofunsaturation is contacted with at least one alpha olefin in the presenceof a metathesis catalyst to provide at least one estolide base oil withat least one fatty acid chain residue having at least one terminal siteof unsaturation, and an olefin product. For example, an estolide with anoleate cap may be contacted with an alpha olefin such as ethene(ethylene) in the presence of a metathesis catalyst to provide anestolide base oil with a truncated cap, and a terminal olefin(1-decene), as shown in Scheme 7:

As described above, the at least one estolide compound can bemetathesized to provide at least one estolide base oil having at leastone fatty acid residue with at least one terminal site of unsaturation.In certain embodiments, the metathesis leaves the at least one estolidecompound substantially intact and/or unchanged, but for the cleavage andshortening of the at least one fatty acid residue. For example, as shownabove, the metathesis of an estolide comprising an oleic acid cap withethene will provide an estolide base oil with a C₁₀ cap, as well as acleaved 1-decene terminal olefin. However, in certain embodiments, thecross metathesis of the at least one estolide compound with an alphaolefin having more than 2 carbons, such as 1-butene, provides a mixtureof products. For example, the cross metathesis of the at least oneestolide compound may provide a mixture of 1-decene and 3-dodecene, andan estolide base oil with individual estolides having a C₁₀ cap with aterminal double bond or a C₁₂ cap with an internal double bond

In certain embodiments, the process of preparing the estolide base oilfurther comprises functionalizing the terminal site of unsaturation ofthe at least one fatty acid residue. In certain embodiments, thefunctionalizing comprises hydrogenating the at least one terminal siteof unsaturation. In certain embodiments, the functionalizing comprisesreacting the at least one terminal site of unsaturation with at leastone carboxylic acid, wherein a covalent bond is formed between an oxygenof a carboxylic group of the at least one carboxylic acid and a carbonof the at least one terminal site of unsaturation. In certainembodiments, the functionalizing comprises halogenating, sulfonating,sulfurizing, or epoxidizing the at least one fatty acid residue. Incertain embodiments, the functionalizing comprises the coupling betweenthe terminal site of unsaturation and an aryl or vinyl halide (e.g.,Heck reaction). In certain embodiments, the functionalizing comprisesthe addition of an aldehyde or ketone to the terminal site ofunsaturation (e.g., Prins reaction). In certain embodiments, thefunctionalizing comprises converting the terminal site of unsaturationinto a carboxylic acid (e.g., Koch reaction). In certain embodiments,the functionalizing comprises exposing the terminal site of unsaturationto further metathesis conditions in the presence of, for example, andacrylate (e.g., methyl acrylate) to provide a terminal ester. In certainembodiments, the functionalizing comprises reacting the terminal site ofunsaturation with water or an alcohol (e.g., under acidic conditions) toform a hydroxyl group or an ether, respectively. In certain embodiments,any of aforementioned functionalizing methods may be accomplished usingany of the methods known by persons of ordinary skill in the art.

In another embodiment is described a process of producing compoundscomprising:

providing at least one first fatty acid reactant and at least one secondfatty acid reactant, wherein the at least one second fatty acid reactanthas at least one terminal site of unsaturation; and

reacting the at least one first fatty acid reactant with the at leastone second fatty acid reactant to provide a compound, wherein a covalentbond is formed between an oxygen of a carboxylic group of the at leastone first fatty acid reactant and a carbon of the at least one terminalsite of unsaturation of the at least one second fatty acid reactant.

In certain embodiments, the at least one first fatty acid reactant isselected from one or more saturated or unsaturated fatty acids. Incertain embodiments, the at least one second fatty acid reactant havingat least one terminal site of unsaturation is selected from unsaturatedfatty acids, unsaturated fatty acid alkyl esters, unsaturated fatty acidglycerides, and unsaturated fatty acid oligomers. In certainembodiments, the at least one second fatty acid reactant having at leastone terminal site of unsaturation is prepared by subjecting a fatty acidsubstrate having at least one internal site of unsaturation to any ofthe cross metathesis conditions previously described herein, such asthose comprising a metathesis catalyst and an alpha olefin (e.g.,ethene). In certain embodiments, the fatty acid substrate is selectedfrom one or more unsaturated fatty acid substrates, such as one or moreunsaturated fatty acid substrates having at least one internal site ofunsaturation selected from one or more triglycerides, one or morediglycerides, one or more monoglycerides, one or more fatty acid alkylesters, or one or more free fatty acids. In certain embodiments, the atleast one second fatty acid reactant is a triglyceride having at leastone terminal site of unsaturation, which may be derived from the crossmetathesis of a triglyceride substrate having at least one internal siteof unsaturation. In certain embodiments, the at least one second fattyacid reactant is a fatty acid having at least one terminal site ofunsaturation, which may be derived from the cross metathesis of a fattyacid ester (e.g., triglyceride) substrate having at least one internalsite of unsaturation and the subsequent liberation of the truncatedfatty acid via glycerine removal. Accordingly, in certain embodiments,the at least one second fatty acid is derived from a process thatincludes cross metathesis. In certain embodiments, the at least onefirst and second fatty acid reactants are fatty acids, wherein the firstand second fatty acids are derived from a process that includesmetathesis.

In certain embodiments, the resulting compound is prepared by reactingthe at least one first fatty acid reactant with the at least one secondfatty acid reactant having at least one terminal site of unsaturation,wherein a covalent bond is formed between an oxygen of a carboxylicgroup of the at least one first fatty acid reactant and a carbon of theat least one terminal site of unsaturation of the at least one secondfatty acid reactant. In certain embodiments, that at least one first andsecond fatty acid reactants both comprise at least one terminal site ofunsaturation. In certain embodiments, the at least one first fatty acidreactant and at least one second fatty acid reactant comprise the samestructure (e.g., C₁₀ fatty acid with a terminal double bond preparedfrom the metathesis of oleic acid with ethene). In certain embodiments,the reacting of the at least one first fatty acid with the at least onesecond fatty acid takes place in the presence of an oligomerizationcatalyst, such as those described below. In certain embodiments, theprocess comprises the oligomerization of one or more free fatty acids.

In certain embodiments, the process of reacting the at least one firstfatty acid reactant with the at least one second fatty acid reactanthaving at least one terminal site of unsaturation provides compoundshaving a high degree of oligomerization and/or polymerization. Forexample, in certain embodiments, it is believed that this high degree ofoligomerization and/or polymerization is possible because each fattyacid reactant links to the hydrocarbyl terminus of another fatty acid,i.e., at the terminal or penultimate carbon of the fatty acid. Thus,unlike the oligomerization of fatty acids having internal sites ofunsaturation, the resulting fatty acid oligomer of unbranched orlightly-branched fatty acids having terminal sites of unsaturation willprovide a steric profile that may be more favorable for furtheroligomerization and increased growth of the molecule. In certainembodiments, this process provides a method for preparing compounds ofFormula III.

In certain embodiments, the oligomerization catalyst comprises one ormore compounds selected from Bronsted acid catalysts and Lewis acidcatalysts. In certain embodiments, the Lewis acid catalyst is selectedfrom one or more triflates (trifluormethanesulfonates) such astransition metal triflates and lanthanide triflates. Suitable triflatesmay include, but are not limited to, AgOTf (silver triflate), Cu(OTf)₂(copper triflate), NaOTf (sodium triflate), Fe(OTf)₂ (iron (II)triflate), Fe(OTf)₃ (iron (III) triflate), LiOTf (lithium triflate),Yb(OTf)₃ (ytterbium triflate), Y(OTf)₃ (yttrium triflate), Zn(OTf)₂(zinc triflate), Ni(OTf)₂ (nickel triflate), Bi(OTf)₃ (bismuthtriflate), La(OTf)₃ (lanthanum triflate), and Sc(OTf)₃ (scandiumtriflate). In certain embodiments, the Lewis acid catalyst is Fe(OTf)₃.In certain embodiments, the Lewis acid catalyst is Bi(OTf)₃. In certainembodiments, the Lewis acid catalyst is Fe(OTf)₂.

In certain embodiments, Lewis acid catalyst comprises one or compoundsselected from metal compounds, such as iron compounds, cobalt compounds,and nickel compounds. In certain embodiments, the metal compound isselected from one or more of FeX_(n) (n=2, 3), Fe(CO)₅, Fe₃(CO)₁₂,Fe(CO)₃(ET), Fe(CO)₃(DE), Fe(DE)₂, CpFeX(CO)₂, [CpFe(CO)₂]₂,[Cp*Fe(CO)₂]₂, Fe(acac)₃, Fe(OAc)_(n) (n=2, 3), CoX₂, CO₂(CO)₈,Co(acac)_(n), (n=2, 3), Co(OAc)₂, CpCO(CO)₂, Cp*Co(CO)₂, NiX₂, Ni(CO)₄,Ni(DE)₂, Ni(acac)₂, and Ni(OAc)₂, wherein X is selected from hydrogen,halogen, hydroxyl, cyano, alkoxy, carboxylato, and thiocyanato; whereinCp is a cyclopentadienyl group; acac is an acetylacetonato group; DE isselected from norbornadienyl, 1,5-cyclooctadienyl, and 1,5-hexadienyl;ET is selected from ethylenyl and cyclooctenyl; and OAc represents anacetate group. In some embodiments, the Lewis acid is an iron compound.In some embodiments, the Lewis acid is an iron compound selected fromone or more of Fe(acac)₃, FeCl₃, Fe₂(SO₄)₃, Fe₂O₃, and FeSO₄.

In addition, or in the alternative, the oligomerization comprises theuse of one or more Bronsted acid catalysts. Exemplary Bronsted acidsinclude, but are not limited to, hydrochloric acid, nitric acid,sulfamic acid, methylsulfamic acid, sulfuric acid, phosphoric acid,perchloric acid, triflic acid, p-toluenesulfonic acid (p-TsOH), andcombinations thereof. In certain embodiments, the Bronsted acid isselected from one or more of sulfamic acid and methylsulfamic acid. Insome embodiments, the Bronsted acid may comprise cation exchange resins,acid exchange resins and/or solid-supported acids. Such materials mayinclude styrene-divinylbenzene copolymer-based strong cation exchangeresins such as Amberlyst® (Rohm & Haas; Philadelphia, Pa.), Dowex® (Dow;Midland, Mich.), CG resins from Resintech, Inc. (West Berlin, N.J.), andLewatit resins such as MonoPlus™ S 100H from Sybron Chemicals Inc.(Birmingham, N.J.). Exemplary solid acid catalysts include cationexchange resins, such as Amberlyst® 15, Amberlyst® 35, Amberlite® 120,Dowex® Monosphere M-31, Dowex® Monosphere DR-2030, and acidic andacid-activated mesoporous materials and natural clays such a kaolinites,bentonites, attapulgites, montmorillonites, and zeolites. Exemplarycatalysts also include organic acids supported on mesoporous materialsderived from polysaccharides and activated carbon, such asStarbon®—supported sulphonic acid catalysts (University of York) likeStarbon® 300, Starbon® 400, and Starbon® 800. Phosphoric acids on solidsupports may also be suitable, such as phosphoric acid supported onsilica (e.g., SPA-2 catalysts sold by Sigma-Aldrich).

In certain embodiments, one or more fluorinated sulfonic acid polymersmay be used as solid-acid catalysts for the processes described herein.These acids are partially or totally fluorinated hydrocarbon polymerscontaining pendant sulfonic acid groups, which may be partially ortotally converted to the salt form. Exemplary sulfonic acid polymersinclude Nafion® perfluorinated sulfonic acid polymers such as Nafion®SAC-13 (E.I. du Pont de Nemours and Company, Wilmington, Del.). Incertain embodiments, the catalyst comprises a Nafion® Super AcidCatalyst, a bead-form strongly acidic resin which is a copolymer oftetrafluoroethylene and perfluoro-3,6-dioxa-4-methyl-7-octene sulfonylfluoride, converted to either the proton (H⁺), or the metal salt form.In some embodiments, the oligomerization process comprises use of one ormore of protic or aprotic catalysts.

In some embodiments, the oligomerization processes are aided by theapplication of electromagnetic energy. In certain embodiments, theelectromagnetic energy used to aid the oligomerization is microwaveelectromagnetic energy. In certain embodiments, for example, applicationof electromagnetic radiation may be applied to reduce the overallreaction time and improve the yield of the compound by conducting thereaction in a microwave reactor in the presence of an oligomerizationcatalyst. In some embodiments, oligomerizing the at least one firstfatty acid reactant with the at least one second fatty acid reactant isconducted in the presence of an oligomerization catalyst (e.g., a Lewisacid) and microwave radiation. In some embodiments, the oligomerizationis conducted in a microwave reactor with Bi(OTf)₃. In some embodiments,the oligomerization is conducted in a microwave reactor with Fe(OTf)₃.In some embodiments, the oligomerization is conducted in a microwavereactor with Fe(OTf)₂.

In some embodiments, depending on the nature of the catalyst and thereaction conditions, it may be desirable to carry out the process at acertain temperature and/or pressure. In some embodiments, for example,suitable temperatures for effecting oligomerization may includetemperatures greater than about 50° C., such as a range of about 50° C.to about 100° C. In some embodiments, the oligomerization is carried outat about 60° C. to about 80° C. In some embodiments, the oligomerizationis carried out, for at least a portion of the time, at about 50° C.,about 52° C., about 54° C., about 56° C., about 58° C., about 60° C.,about 62° C., about 64° C., about 66° C., about 68° C., about 70° C.,about 72° C., about 74° C., about 76° C., about 78° C., about 80° C.,about 82° C., about 84° C., about 86° C., about 88° C., about 90° C.,about 92° C., about 94° C., about 96° C., about 98° C., and about 100°C. In some embodiments, the oligomerization is carried out, for at leasta period of time, at a temperature of no greater than about 52° C.,about 54° C., about 56° C., about 58° C., about 60° C., about 62° C.,about 64° C., about 66° C., about 68° C., about 70° C., about 72° C.,about 74° C., about 76° C., about 78° C., about 80° C., about 82° C.,about 84° C., about 86° C., about 88° C., about 90° C., about 92° C.,about 94° C., about 96° C., about 98° C., or about 100° C.

In some embodiments, suitable oligomerization conditions may includereactions that are carried out at a pressure of less than 1 atm abs(absolute), such at less than about 250 torr abs, less than about 100torr abs, less than about 50 torr abs, or less than about 25 torr abs.In some embodiments, oligomerization is carried out at a pressure ofabout 1 torr abs to about 20 torr abs, or about 5 torr abs to about 15torr abs. In some embodiments, oligomerization, for at least a period oftime, is carried out at a pressure of greater than about 5, about 10,about 15, about 20, about 25, about 30, about 35, about 40, about 45,about 50, about 55, about 60, about 65, about 70, about 75, about 80,about 85, about 90, about 95, about 100, about 105, about 110, about115, about 120, about 125, about 130, about 135, about 140, about 145,about 150, about 155, about 160, about 165, about 170, about 175, about180, about 185, about 190, about 195, about 200, about 205, about 210,about 215, about 220, about 225, about 230, about 235, about 240, about245, and about 250 torrs abs. In some embodiments, oligomerization, forat least a period of time, is carried out at a pressure of less thanabout 5, about 10, about 15, about 20, about 25, about 30, about 35,about 40, about 45, about 50, about 55, about 60, about 65, about 70,about 75, about 80, about 85, about 90, about 95, about 100, about 105,about 110, about 115, about 120, about 125, about 130, about 135, about140, about 145, about 150, about 155, about 160, about 165, about 170,about 175, about 180, about 185, about 190, about 195, about 200, about205, about 210, about 215, about 220, about 225, about 230, about 235,about 240, about 245, or about 250 torrs abs.

In certain embodiments, it may be desirable to esterify a free fattyacid compound in the presence of at least one alcohol. Accordingly, incertain embodiments, the processes described herein further comprise thestep of esterifying the resulting free acid estolide in the presence ofat least one esterification catalyst. Suitable esterification catalystsmay include one or more Lewis acids and/or Bronsted acids selected from,for example, AgOTf, Cu(OTf)₂, Fe(OTf)₂, Fe(OTf)₃, NaOTf, LiOTf,Yb(OTf)₃, Y(OTf)₃, Zn(OTf)₂, Ni(OTf)₂, Bi(OTf)₃, La(OTf)₃, Sc(OTf)₃,hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid,perchloric acid, triflic acid, p-TsOH, and combinations thereof. Incertain embodiments, the esterification catalyst is selected from cationexchange resins, acid exchange resins and/or solid-supported acids, suchas those previously described herein. In some embodiments, theesterification catalyst may comprise a strong Lewis acid such as BF₃etherate. In some embodiments, the Lewis acid of the oligomerizing stepand the esterification catalyst will be the same, such as Bi(OTf)₃. Insome embodiments, the esterification is conducted in the presence ofmicrowave radiation.

In some embodiments, the esterification catalyst may comprise a Lewisacid catalyst, for example, at least one metal compound selected fromtitanium compounds, tin compounds, zirconium compounds, hafniumcompounds, and combinations thereof. In some embodiments, the Lewis acidesterification catalyst is at least one titanium compound selected fromTiCl₄ and Ti(OCH₂CH₂CH₂CH₃)₄ (titanium (IV) butoxide). In someembodiments, the Lewis acid esterification catalyst is at least one tincompound selected from Sn(O₂CCO₂) (tin (II) oxalate), SnO, and SnCl₂. Insome embodiments, the Lewis acid esterification catalyst is at least onezirconium compound selected from ZrCl₄, ZrOCl₂, ZrO(NO₃)₂, ZrO(SO₄), andZrO(CH₃COO)₂. In some embodiments, the Lewis acid esterificationcatalyst is at least one hafnium compound selected from HfCl₂ andHfOCl₂. Unless stated otherwise, all metal compounds and catalystsdiscussed herein should be understood to include their hydrate andsolvate forms. For example, in some embodiments, the Lewis acidesterification catalyst may be selected from ZrOCl₂.8H₂O andZrOCl₂.2THF, or HfOCl₂.2THF and HfOCl₂.8H₂O.

The present disclosure further relates to methods of making compoundsaccording to Formula I, II, III, and V. By way of example, the reactionof an unsaturated fatty acid with an organic acid and the esterificationof the resulting free acid estolide are illustrated and discussed in thefollowing Schemes 8 and 9. The particular structural formulas used toillustrate the reactions correspond to those for synthesis of compoundsaccording to Formula V, prior to metathesis of the Formula V precursor;however, the methods apply equally to the synthesis of compoundsaccording to Formula I, II, and III, with use of compounds havingstructures corresponding to R₃ and R₄ with a reactive terminal site ofunsaturation.

As illustrated below, compound 100 represents an unsaturated fatty acidthat may serve as the basis for preparing the estolide compoundsdescribed herein.

In Scheme 8, wherein x is, independently for each occurrence, an integerselected from 0 to 20, y is, independently for each occurrence, aninteger selected from 0 to 20, n is an integer greater than or equal to1, and R₁ is an optionally substituted alkyl that is saturated orunsaturated, and branched or unbranched, unsaturated fatty acid 100 maybe combined with compound 102 and a proton from a proton source to formfree acid estolide 104. In certain embodiments, compound 102 is notincluded, and unsaturated fatty acid 100 may be exposed alone to acidicconditions to form free acid estolide 104, wherein R₁ would represent anunsaturated alkyl group. In certain embodiments, if compound 102 isincluded in the reaction, R₁ may represent one or more optionallysubstituted alkyl residues that are saturated or unsaturated andbranched or unbranched. Any suitable proton source may be implemented tocatalyze the formation of free acid estolide 104, including but notlimited to homogenous acids and/or strong acids like hydrochloric acid,sulfuric acid, perchloric acid, nitric acid, triflic acid, and the like.

Similarly, in Scheme 9, wherein x is, independently for each occurrence,an integer selected from 0 to 20, y is, independently for eachoccurrence, an integer selected from 0 to 20, n is an integer greaterthan or equal to 1, and R₁ and R₂ are each an optionally substitutedalkyl that is saturated or unsaturated, and branched or unbranched, freeacid estolide 104 may be esterified by any suitable procedure known tothose of skilled in the art, such as acid-catalyzed reduction withalcohol 202, to yield esterified estolide 204. Other exemplary methodsmay include other types of Fischer esterification, such as those usingLewis acid catalysts such as BF₃.

As discussed above, in certain embodiments, the compounds describedherein may have improved properties which render them useful as basestocks for biodegradable lubricant applications. Such applications mayinclude, without limitation, crankcase oils, gearbox oils, hydraulicfluids, drilling fluids, two-cycle engine oils, greases, and the like.Other suitable uses may include marine applications, wherebiodegradability and toxicity are of concern. In certain embodiments,the nontoxic nature of certain estolides described herein may also makethem suitable for use as lubricants in the cosmetic and food industries.

In certain embodiments, the estolide compounds may meet or exceed one ormore of the specifications for certain end-use applications, without theneed for conventional additives. For example, in certain instances,high-viscosity lubricants, such as those exhibiting a kinematicviscosity of greater than about 120 cSt at 40° C., or even greater thanabout 200 cSt at 40° C., may be desired for particular applications suchas gearbox or wind turbine lubricants. Prior-known lubricants with suchproperties typically also demonstrate an increase in pour point asviscosity increases, such that prior lubricants may not be suitable forsuch applications in colder environments. However, in certainembodiments, the counterintuitive properties of certain compoundsdescribed herein (e.g., increased EN provides estolides with higherviscosities while retaining, or even decreasing, the oil's pour point)may make higher-viscosity estolides particularly suitable for suchspecialized applications.

Similarly, the use of prior-known lubricants in colder environments maygenerally result in an unwanted increase in a lubricant's viscosity.Thus, depending on the application, it may be desirable to uselower-viscosity oils at lower temperatures. In certain circumstances,low-viscosity oils may include those exhibiting a viscosity of lowerthan about 50 cSt at 40° C., or even about 40 cSt at 40° C. Accordingly,in certain embodiments, the low-viscosity estolides described herein mayprovide end users with a suitable alternative to high-viscositylubricants for operation at lower temperatures.

In some embodiments, it may be desirable to prepare lubricantcompositions comprising an estolide base stock. For example, in certainembodiments, the compounds described herein may be blended with one ormore additives selected from polyalphaolefins, synthetic esters,polyalkylene glycols, mineral oils (Groups I, II, and III), pour pointdepressants, viscosity modifiers, anti-corrosives, antiwear agents,detergents, dispersants, colorants, antifoaming agents, anddemulsifiers. In addition, or in the alternative, in certainembodiments, the estolides described herein may be co-blended with oneor more synthetic or petroleum-based oils to achieve desired viscosityand/or pour point profiles. In certain embodiments, certain estolidesdescribed herein also mix well with gasoline, so that they may be usefulas fuel components or additives.

In certain embodiments, the compounds described herein may be consideredoligomeric and/or polymeric in nature, and may have use in applicationsthat typically implement polymers. In certain embodiments, the compoundsmay be useful as lubricants, such as high-viscosity lubricants. Incertain embodiments, the compounds may comprise a film or film-likematerial that may be useful in coating technologies (e.g., inks, paints,film coverings). In certain embodiments, the compounds may comprise amaterial that is suitable as a plastic additive or plastic alternative.For example, in certain embodiments, the material may be hardened and/orshaped into an article of manufacture, such as housewares (e.g.,disposable utensils, storage bins). In certain embodiments, thematerials are readily biodegradable and may serve as a substitute forplastics.

In all of the foregoing examples, the compounds described may be usefulalone, as mixtures, or in combination with other compounds,compositions, and/or materials.

Methods for obtaining the novel compounds described herein will beapparent to those of ordinary skill in the art, suitable proceduresbeing described, for example, in the examples below, and in thereferences cited herein.

EXAMPLES Analytics

Nuclear Magnetic Resonance:

NMR spectra were collected using a Bruker Avance 500 spectrometer withan absolute frequency of 500.113 MHz at 300 K using CDCl₃ as thesolvent. Chemical shifts were reported as parts per million fromtetramethylsilane. The formation of a secondary ester link between fattyacids, indicating the formation of estolide, was verified with ¹H NMR bya peak at about 4.84 ppm.

Estolide Number (EN):

The EN was measured by GC analysis. It should be understood that the ENof a composition specifically refers to EN characteristics of anyestolide compounds present in the composition. Accordingly, an estolidecomposition having a particular EN may also comprise other components,such as natural or synthetic additives, other non-estolide base oils,fatty acid esters, e.g., triglycerides, and/or fatty acids, but the ENas used herein, unless otherwise indicated, refers to the value for theestolide fraction of the estolide composition.

Iodine Value (IV):

The iodine value is a measure of the degree of total unsaturation of anoil. IV is expressed in terms of centigrams of iodine absorbed per gramof oil sample. Therefore, the higher the iodine value of an oil thehigher the level of unsaturation is of that oil. The IV may be measuredand/or estimated by GC analysis. Where a composition includesunsaturated compounds other than estolides as set forth in Formula I,II, III, and V, the estolides can be separated from other unsaturatedcompounds present in the composition prior to measuring the iodine valueof the constituent estolides. For example, if a composition includesunsaturated fatty acids or triglycerides comprising unsaturated fattyacids, these can be separated from the estolides present in thecomposition prior to measuring the iodine value for the one or moreestolides.

Acid Value:

The acid value is a measure of the total acid present in an oil. Acidvalue may be determined by any suitable titration method known to thoseof ordinary skill in the art. For example, acid values may be determinedby the amount of KOH that is required to neutralize a given sample ofoil, and thus may be expressed in terms of mg KOH/g of oil.

Gas Chromatography (GC):

GC analysis was performed to evaluate the estolide number (EN) andiodine value (IV) of the estolides. This analysis was performed using anAgilent 6890N series gas chromatograph equipped with a flame-ionizationdetector and an autosampler/injector along with an SP-2380 30 m×0.25 mmi.d. column.

The parameters of the analysis were as follows: column flow at 1.0mL/min with a helium head pressure of 14.99 psi; split ratio of 50:1;programmed ramp of 120-135° C. at 20° C./min, 135-265° C. at 7° C./min,hold for 5 min at 265° C.; injector and detector temperatures set at250° C.

Measuring EN and IV by GC:

To perform these analyses, the fatty acid components of an estolidesample were reacted with MeOH to form fatty acid methyl esters by amethod that left behind a hydroxy group at sites where estolide linkswere once present. Standards of fatty acid methyl esters were firstanalyzed to establish elution times.

Sample Preparation:

To prepare the samples, 10 mg of estolide was combined with 0.5 mL of0.5M KOH/MeOH in a vial and heated at 100° C. for 1 hour. This wasfollowed by the addition of 1.5 mL of 1.0 M H₂SO₄/MeOH and heated at100° C. for 15 minutes and then allowed to cool to room temperature. One(1) mL of H₂O and 1 mL of hexane were then added to the vial and theresulting liquid phases were mixed thoroughly. The layers were thenallowed to phase separate for 1 minute. The bottom H₂O layer was removedand discarded. A small amount of drying agent (Na₂SO₄ anhydrous) wasthen added to the organic layer after which the organic layer was thentransferred to a 2 mL crimp cap vial and analyzed.

EN Calculation:

The EN is measured as the percent hydroxy fatty acids divided by thepercent non-hydroxy fatty acids. As an example, a dimer estolide wouldresult in half of the fatty acids containing a hydroxy functional group,with the other half lacking a hydroxyl functional group. Therefore, theEN would be 50% hydroxy fatty acids divided by 50% non-hydroxy fattyacids, resulting in an EN value of 1 that corresponds to the singleestolide link between the capping fatty acid and base fatty acid of thedimer.

IV Calculation:

The iodine value is estimated by the following equation based on ASTMMethod D97 (ASTM International, Conshohocken, Pa.):

${IV} = {\sum{100 \times \frac{A_{f} \times {MW}_{I} \times {db}}{{MW}_{f}}}}$

-   -   A_(f)=fraction of fatty compound in the sample    -   MW₁=253.81, atomic weight of two iodine atoms added to a double        bond    -   db=number of double bonds on the fatty compound    -   MW_(f)=molecular weight of the fatty compound

The properties of exemplary estolide compounds and compositionsdescribed herein are identified in the following examples and tables.

Other Measurements:

Except as otherwise described, pour point is measured by ASTM MethodD97-96a, cloud point is measured by ASTM Method D2500,viscosity/kinematic viscosity is measured by ASTM Method D445-97,viscosity index is measured by ASTM Method D2270-93 (Reapproved 1998),specific gravity is measured by ASTM Method D4052, flash point ismeasured by ASTM Method D92, evaporative loss is measured by ASTM MethodD5800, vapor pressure is measured by ASTM Method D5191, and acuteaqueous toxicity is measured by Organization of Economic Cooperation andDevelopment (OECD) 203.

Example 1

The acid catalyst reaction was conducted in a 50 gallon PfaudlerRT-Series glass-lined reactor. Oleic acid (65 Kg, OL 700, Twin Rivers)was added to the reactor with 70% perchloric acid (992.3 mL, AldrichCat#244252) and heated to 60° C. in vacuo (10 torr abs) for 24 hrs whilecontinuously being agitated. After 24 hours the vacuum was released.2-Ethylhexanol (29.97 Kg) was then added to the reactor and the vacuumwas restored. The reaction was allowed to continue under the sameconditions (60° C., 10 torr abs) for 4 more hours. At which time, KOH(645.58 g) was dissolved in 90% ethanol/water (5000 mL, 90% EtOH byvolume) and added to the reactor to quench the acid. The solution wasthen allowed to cool for approximately 30 minutes. The contents of thereactor were then pumped through a 1 micron (μ) filter into anaccumulator to filter out the salts. Water was then added to theaccumulator to wash the oil. The two liquid phases were thoroughly mixedtogether for approximately 1 hour. The solution was then allowed tophase separate for approximately 30 minutes. The water layer was drainedand disposed of. The organic layer was again pumped through a 1μ filterback into the reactor. The reactor was heated to 60° C. in vacuo (10torr abs) until all ethanol and water ceased to distill from solution.The reactor was then heated to 100° C. in vacuo (10 torr abs) and thattemperature was maintained until the 2-ethylhexanol ceased to distillfrom solution. The remaining material was then distilled using a Myers15 Centrifugal Distillation still at 200° C. under an absolute pressureof approximately 12 microns (0.012 torr) to remove all monoestermaterial leaving behind estolides (Ex. 1). Certain data are reportedbelow in Tables 1 and 6.

Example 2

The acid catalyst reaction was conducted in a 50 gallon PfaudlerRT-Series glass-lined reactor. Oleic acid (50 Kg, OL 700, Twin Rivers)and whole cut coconut fatty acid (18.754 Kg, TRC 110, Twin Rivers) wereadded to the reactor with 70% perchloric acid (1145 mL, AldrichCat#244252) and heated to 60° C. in vacuo (10 torr abs) for 24 hrs whilecontinuously being agitated. After 24 hours the vacuum was released.2-Ethylhexanol (34.58 Kg) was then added to the reactor and the vacuumwas restored. The reaction was allowed to continue under the sameconditions (60° C., 10 torr abs) for 4 more hours. At which time, KOH(744.9 g) was dissolved in 90% ethanol/water (5000 mL, 90% EtOH byvolume) and added to the reactor to quench the acid. The solution wasthen allowed to cool for approximately 30 minutes. The contents of thereactor were then pumped through a 1μ filter into an accumulator tofilter out the salts. Water was then added to the accumulator to washthe oil. The two liquid phases were thoroughly mixed together forapproximately 1 hour. The solution was then allowed to phase separatefor approximately 30 minutes. The water layer was drained and disposedof. The organic layer was again pumped through a 1μ filter back into thereactor. The reactor was heated to 60° C. in vacuo (10 torr abs) untilall ethanol and water ceased to distill from solution. The reactor wasthen heated to 100° C. in vacuo (10 torr abs) and that temperature wasmaintained until the 2-ethylhexanol ceased to distill from solution. Theremaining material was then distilled using a Myers 15 CentrifugalDistillation still at 200° C. under an absolute pressure ofapproximately 12 microns (0.012 torr) to remove all monoester materialleaving behind estolides (Ex. 2). Certain data are reported below inTables 2 and 5.

Example 3

The estolides produced in Example 1 (Ex. 1) were subjected todistillation conditions in a Myers 15 Centrifugal Distillation still at300° C. under an absolute pressure of approximately 12 microns (0.012torr). This resulted in a primary distillate having a lower EN average(Ex. 3A), and a distillation residue having a higher EN average (Ex.3B). Certain data are reported below in Tables 1 and 6.

TABLE 1 Pour Iodine Estolide Point Value Base Stock EN (° C.) (cg/g) Ex.3A 1.35 −32 31.5 Ex. 1 2.34 −40 22.4 Ex. 3B 4.43 −40 13.8

Example 4

Estolides produced in Example 2 (Ex. 2) were subjected to distillationconditions in a Myers 15 Centrifugal Distillation still at 300° C. underan absolute pressure of approximately 12 microns (0.012 torr). Thisresulted in a primary distillate having a lower EN average (Ex. 4A), anda distillation residue having a higher EN average (Ex. 4B). Certain dataare reported below in Tables 2 and 7.

TABLE 2 Estolide Iodine Base Stock EN Pour Point (° C.) Value (cg/g) Ex.4A 1.31 −30 13.8 Ex. 2 1.82 −33 13.2 Ex. 4B 3.22 −36 9.0

Example 5

Estolides were made according to the method set forth in Example 1,except that the 2-ethylhexanol esterifying alcohol used in Example 1 wasreplaced with various other alcohols. Alcohols used for esterificationinclude those identified in Table 3 below. The properties of theresulting estolides are set forth in Table 7.

TABLE 3 Alcohol Structure Jarcol™ I-18CG iso-octadecanol Jarcol™ I-122-butyloctanol Jarcol™ I-20 2-octyldodecanol Jarcol™ I-16 2-hexyldecanolJarcol™ 85BJ cis-9-octadecen-1-ol Fineoxocol ^(®) 180

Jarcol™ I-18T 2-octyldecanol

Example 6

Estolides were made according to the method set forth in Example 2,except the 2-ethylhexanol esterifying alcohol was replaced withisobutanol. The properties of the resulting estolides are set forth inTable 7.

Example 7

Estolides of Formula I, II, III, and V are prepared according to themethod set forth in Examples 1 and 2, except that the 2-ethylhexanolesterifying alcohol is replaced with various other alcohols. Alcohols tobe used for esterification include those identified in Table 4 below.Esterifying alcohols to be used, including those listed below, may besaturated or unsaturated, and branched or unbranched, or substitutedwith one or more alkyl groups selected from methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl,neopentyl, hexyl, isohexyl, and the like, to form a branched orunbranched residue at the R₂ position. Examples of combinations ofesterifying alcohols and R₂ Substituents are set forth below in Table 4:

TABLE 4 Alcohol R₂ Substituents C₁ alkanol methyl C₂ alkanol ethyl C₃alkanol n-propyl, isopropyl C₄ alkanol n-butyl, isobutyl, sec-butyl C₅alkanol n-pentyl, isopentyl neopentyl C₆ alkanol n-hexyl, 2-methylpentyl, 3- methyl pentyl, 2,2-dimethyl butyl, 2,3-dimethyl butyl C₇alkanol n-heptyl and other structural isomers C₈ alkanol n-octyl andother structural isomers C₉ alkanol n-nonyl and other structural isomersC₁₀ alkanol n-decanyl and other structural isomers C₁₁ alkanoln-undecanyl and other structural isomers C₁₂ alkanol n-dodecanyl andother structural isomers C₁₃ alkanol n-tridecanyl and other structuralisomers C₁₄ alkanol n-tetradecanyl and other structural isomers C₁₅alkanol n-pentadecanyl and other structural isomers C₁₆ alkanoln-hexadecanyl and other structural isomers C₁₇ alkanol n-heptadecanyland other structural isomers C₁₈ alkanol n-octadecanyl and otherstructural isomers C₁₉ alkanol n-nonadecanyl and other structuralisomers C₂₀ alkanol n-icosanyl and other structural isomers C₂₁ alkanoln-heneicosanyl and other structural isomers C₂₂ alkanol n-docosanyl andother structural isomers

TABLE 5 ASTM PROPERTY ADDITIVES METHOD Ex. 4A Ex. 2 Ex. 4B Color None —Light Amber Amber Gold Specific Gravity (15.5° C.), g/ml None D 40520.897 0.904. 0.912 Viscosity - Kinematic at 40° C., cSt None D 445 32.565.4 137.3 Viscosity - Kinematic at 100° C., cSt None D 445 6.8 11.319.9 Viscosity Index None D 2270 175 167 167 Pour Point, ° C. None D 97−30 −33 −36 Cloud Point, ° C. None D 2500 −30 −32 −36 Flash Point, ° C.None D 92 278 264 284 Fire Point, ° C. None D 92 300 300 320 EvaporativeLoss (NOACK), wt. % None D 5800 1.9 1.4 0.32 Vapor Pressure - Reid(RVP), psi None D 5191 ≈0 ≈0 ≈0

TABLE 6 ASTM PROPERTY ADDITIVES METHOD Ex. 3A Ex. 1 Ex. 3B Color None —Light Amber Amber Gold Specific Gravity (15.5° C.), g/ml None D 40520.897 0.906 0.917 Viscosity - Kinematic at 40° C., cSt None D 445 40.991.2 211.6 Viscosity - Kinematic at 100° C., cSt None D 445 8.0 14.827.8 Viscosity Index None D 2270 172 170 169 Pour Point, ° C. None D 97−32 −40 −40 Cloud Point, ° C. None D 2500 −32 −33 −40 Flash Point, ° C.None D 92 278 286 306 Fire Point, ° C. None D 92 300 302 316 EvaporativeLoss (NOACK), wt. % None D 5800 1.4 0.8 0.3 Vapor Pressure - Reid (RVP),psi None D 5191 ≈0 ≈0 ≈0

TABLE 7 Example Estimated EN Pour Pt. Cloud Pt. Visc. @ Visc. @ Visc. #Alcohol (approx.) ° C. ° C. 40° C. 100° C. Index 8 Jarcol ™ I-18CG2.0-2.6 −15 −13 103.4 16.6 174 8 Jarcol ™ I-12 2.0-2.6 −39 −40 110.916.9 166 8 Jarcol ™ I-20 2.0-2.6 −42 <−42 125.2 18.5 166 8 Jarcol ™ I-162.0-2.6 −51 <−51 79.7 13.2 168 8 Jarcol ™ 85BJ 2.0-2.6 −15 −6 123.8 19.5179 8 Fineoxocol ® 180 2.0-2.6 −39 −41 174.2 21.1 143 8 Jarcol ™ I-18T2.0-2.6 −42 <−42 130.8 19.2 167 8 Isobutanol 2.0-2.6 −36 −36 74.1 12.6170 9 Isobutanol 1.5-2.2 −36 −36 59.5 10.6 170

Example 8

Saturated and unsaturated estolides having varying acid values weresubjected to several corrosion and deposit tests. These tests includedthe High Temperature Corrosion Bench Test (HTCBT) for several metals,the ASTM D130 corrosion test, and the MHT-4 TEOST (ASTM D7097) test forcorrelating piston deposits. The estolides tested having higher acidvalues (0.67 mg KOH/g) were produced using the method set forth inExamples 1 and 4 for producing Ex. 1 and Ex. 4A (Ex.1* and Ex.4A*below). The estolides tested having lower acid values (0.08 mg KOH/g)were produced using the method set forth in Examples 1 and 4 forproducing Ex. 1 and Ex. 4A except the crude free-acid estolide wasworked up and purified prior to esterification with BF₃.OET₂ (0.15equiv.; reacted with estolide and 2-EH in Dean Stark trap at 80° C. invacuo (10 torr abs) for 12 hrs while continuously being agitated; crudereaction product washed 4× H₂O; excess 2-EH removed by heating washedreaction product to 140° C. in vacuo (10 torr abs) for 1 hr) (Ex.4A#below). Estolides having an IV of 0 were hydrogenated via 10 wt. %palladium embedded on carbon at 75° C. for 3 hours under a pressurizedhydrogen atmosphere (200 psig) (Ex.4A*H and Ex.4A#H below) The corrosionand deposit tests were performed with a Dexos™ additive package. Resultswere compared against a mineral oil standard:

TABLE 8 Ex. 1* Ex. 4A* Ex. 4A*H Ex. 4A# Ex. 4A#H Standard EstolideEstolide Estolide Estolide Estolide Acid Value (mg KOH/g) — ~0.7 0.670.67 0.08 0.08 Iodine Value (IV) — ~45 16 0 16 0 HTCBT Cu 13 739 279 609.3 13.6 HTCBT Pd 177 11,639 1,115 804 493 243 HTCBT Sn 0 0 0 0 0 0 ASTMD130 1A 4B 3A 1B 1A 1A MHT-4 18 61 70 48 12 9.3

Example 9

“Ready” and “ultimate” biodegradability of the estolide produced in Ex.1 was tested according to standard OECD procedures. Results of the OECDbiodegradability studies are set forth below in Table 9:

TABLE 9 301D 28-Day 302D Assay (% degraded) (% degraded) Canola Oil 86.978.9 Ex. 1 64.0 70.9 Base Stock

Example 10

The Ex. 1 estolide base stock from Example 1 was tested under OECD 203for Acute Aquatic Toxicity. The tests showed that the estolides arenontoxic, as no deaths were reported for concentration ranges of 5,000mg/L and 50,000 mg/L.

Example 11

Estolides prepared according to the method set forth in Example 1 (20mol) and a second-generation Grubbs' catalyst (e.g., C827, 25 ppm) areadded to a Parr Reactor and degassed with argon for 1 hr. 1-Butene isadded while heating to 60° C. while keeping the pressure of the reactionbetween about 25 to about 60 psi. The 1-butene is added using a one-waycheck valve to prevent backflow into the 1-butene cylinder. After 4 hrs,the pressure is released and vented into the fume hood. After allowingthe reactor to cool to room temperature, a 50 ml 1Mtris-hydroxymethylphopshine (THMP) solution in isopropanol (IPA) (50 molequiv.) is added, and the reactor is degassed with argon and heated to60° C. for 18 hrs. The reactor is then again allowed to cool to roomtemperature. The crude reaction product is then washed with water andbrine. The washed reaction product is them dried over sodium sulfate,filtered, and distilled to provide 1-decene, 3-dodecene, estolideshaving a C₁₀ cap with a terminal double bond, and estolides having a C₁₂cap with an internal double bond.

Example 12

Methyl oleate (20 mol) and a second-generation Grubbs' catalyst (e.g.,C827, 25 ppm) are added to a Parr Reactor and degassed with argon for 1hr. 1-Butene is added while heating to 60° C. while keeping the pressureof the reaction between about 25 to about 60 psi. The 1-butene is addedusing a one-way check valve to prevent backflow into the 1-butenecylinder. After 4 hrs, the pressure is released and vented into the fumehood. After allowing the reactor to cool to room temperature, a 50 ml 1Mtris-hydroxymethylphosphine (THMP) solution in isopropanol (IPA) (50 molequiv.) is added, and the reactor is degassed with argon and heated to60° C. for 18 hrs. The reactor is then again allowed to cool to roomtemperature. The crude reaction product is then washed with water andbrine. The washed reaction product is them dried over sodium sulfate,filtered, and distilled to provide 1-decene, 3-dodecene, 9-decenoic acidmethyl ester, and 9-dodecenoic acid methyl ester.

The 9-dodecenoic acid methyl ester is then hydrolyzed under basicconditions (reflux with an excess of dilute aqueous NaOH), followed byremoval of methanol. The resulting aqueous solution is then treated withan excess of dilute HCl, and the solution is distilled to provide9-dodecenoic acid. Estolides are then prepared according to the methodsset forth in Examples 1 and 2, wherein the oleic acid is replaced with9-dodecenoic acid.

Example 13

9-decenoic acid methyl ester prepared according to the method set forthin Example 12 is isolated then hydrolyzed under basic conditions (refluxwith an excess of dilute aqueous NaOH), followed by removal of methanol.The resulting aqueous solution is then treated with an excess of diluteHCl, and the solution is distilled to provide 9-decenoic acid. Oligomersare then prepared according to the methods set forth in Examples 1 and2, wherein the oleic acid is replaced with 9-decenoic acid.

Example 14

Compounds are prepared according to the methods set forth in Example 12,except methyl oleate is replaced with high-oleic soybean oil (Vistive®Gold, Monsanto Co.) to give a metathesized triglyceride intermediate,which is subsequently hydrolyzed to provide 9-decenoic acid and9-dodecenoic acid. Estolides are then prepared according to the methodsset forth in Examples 1 and 2, wherein oleic acid is replaced with9-decenoic acid and 9-dodecenoic acid.

Example 15

Compounds are prepared according to the methods set forth in Examples 12and 14, except 1-butene is replaced with ethene to provide 1-decene and9-decenoic acid esters as products. The esters are hydrolyzed, andestolides are prepared according to the methods set forth in Examples 1and 2, wherein oleic acid is replaced with 9-decenoic acid.

Example 16

Compounds are prepared according to the methods set forth in Examples12-15. The resulting products are then hydrogenated via 10 wt. %palladium embedded on carbon at 75° C. for 3 hours under a pressurizedhydrogen atmosphere (200 psig) to provide saturated oligomericcompounds.

The invention claimed is:
 1. At least one compound according to FormulaIII:

wherein n is an integer selected from 0 to 20; R₁ is an unsubstituted,branched or unbranched C₇ to C₁₇ alkyl that is saturated or unsaturated;R₂ is hydrogen; and R₃ and R₄, independently for each occurrence, areselected from

wherein R₃ and R₄ are unsubstituted and z is
 7. 2. The at least onecompound according to claim 1, wherein R₁ is selected from the structureof Formula IV:

wherein w is an integer selected from 5 to
 7. 3. The at least onecompound according to claim 2, wherein w is
 7. 4. The at least onecompound according to claim 1, wherein R₁ is saturated and unbranched.5. The at least one compound according to claim 1, wherein n is aninteger selected from 1 to
 20. 6. At least one compound according toFormula III:

wherein n is an integer selected from 1 to 20; R₁ is an unsubstituted,branched or unbranched C₁ to C₂₂ alkyl that is saturated or unsaturated;R₂ is an unsubstituted, branched or unbranched C₁ to C₂₂ alkyl that issaturated or unsaturated; and R₃ and R₄, independently for eachoccurrence, are selected from

wherein R₃ and R₄ are unsubstituted and z is, independently for eachoccurrence, an integer selected from 7 and
 8. 7. The at least onecompound according to claim 6, wherein R₁ is selected from the structureof Formula IV:

wherein w is an integer selected from 0 to
 13. 8. The at least onecompound according to claim 7, wherein w is an integer selected from 5to
 7. 9. The at least one compound according to claim 8, wherein w is 7.10. The at least one compound according to claim 6, wherein R₁ issaturated and unbranched.
 11. The at least one compound according toclaim 6, wherein z is
 7. 12. The at least one compound according toclaim 11, wherein R₁ is an unsubstituted, branched or unbranched C₇ toC₁₇ alkyl that is saturated or unsaturated.
 13. The at least onecompound according to claim 12, wherein R₁ is saturated and unbranched.14. The at least one compound according to claim 13, wherein R₁ is a C₉alkyl.
 15. The at least one compound according to claim 6, wherein z is8.
 16. The at least one compound according to claim 15, wherein R₁ is anunsubstituted, branched or unbranched C₇ to C₁₇ alkyl that is saturatedor unsaturated.
 17. The at least one compound according to claim 16,wherein R₁ is saturated and unbranched.
 18. The at least one compoundaccording to claim 17, wherein R₁ is a C₁₀ alkyl.
 19. The at least onecompound according to claim 6, wherein R₂ is a branched C₆ to C₁₂ alkylthat is saturated.
 20. At least one compound according to Formula III:

wherein n is an integer selected from 0 to 20; R₁ is an unsubstituted,branched or unbranched C₇ to C₁₇ alkyl that is saturated or unsaturated;R₂ is an unsubstituted, branched or unbranched C₁ to C₂₂ alkyl that issaturated or unsaturated; and R₃ and R₄, independently for eachoccurrence, are selected from

wherein R₃ and R₄ are unsubstituted and z is
 8. 21. The at least onecompound according to claim 20, wherein R₁ is a C₇ to C₁₇ alkyl havingat least one terminal site of unsaturation.
 22. The at least onecompound according to claim 21, wherein R₁ is a C₁₀ alkyl.
 23. The atleast one compound according to claim 20, wherein R₁ is saturated andunbranched.
 24. The at least one compound according to claim 20, whereinn is
 0. 25. The at least one compound according to claim 20, wherein nis
 1. 26. The at least one compound according to claim 20, wherein R₂ isa branched C₆ to C₁₂ alkyl that is saturated.
 27. A compositioncomprising: an additive selected from at least one of a polyalphaolefin,a polyalkylene glycol, a mineral oil, a pour point depressant, aviscosity modifier, an anti-corrosive agent, an antiwear agent, adetergent, an antifoaming agent, or a demulsifier; and at least onecompound selected from compounds of Formula III:

wherein n is an integer selected from 0 to 20; R₁ is an unsubstituted,branched or unbranched C₁ to C₂₂ alkyl that is saturated or unsaturated;R₂ is selected from hydrogen and an unsubstituted, branched orunbranched C₁ to C₂₂ alkyl that is saturated or unsaturated; and R₃ andR₄, independently for each occurrence, are selected from

wherein R₃ and R₄ are unsubstituted and z is, independently for eachoccurrence, an integer selected from 7 and
 8. 28. The compositionaccording to claim 27, wherein R₁ is a C₇ to C₁₇ alkyl having at leastone terminal site of unsaturation.
 29. The composition according toclaim 28, wherein R₁ is a C₉ alkyl.
 30. The composition according toclaim 28, wherein R₁ is a C₁₀ alkyl.
 31. The composition according toclaim 27, wherein R₁ is saturated and unbranched.
 32. The compositionaccording to claim 27, wherein R₁ is an unsubstituted, branched orunbranched C₇ to C₁₇ alkyl that is saturated.
 33. The compositionaccording to claim 27, R₂ is an unsubstituted, branched or unbranched C₁to C₂₂ alkyl that is saturated or unsaturated.
 34. The compositionaccording to claim 27, wherein R₂ is a branched C₆ to C₁₂ alkyl that issaturated.
 35. The composition according to claim 27, wherein n is 0.36. The composition according to claim 27, wherein n is
 1. 37. Thecomposition according to claim 33, wherein R₂ is saturated.